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NPTEL – Chemical Engineering – Catalyst Science and Technology

Lecture 5
Solid catalysts
Catalyst components
A solid catalyst consists of mainly three components :

1. Catalytic agent
2. Support /carrier
3. Promoters and Inhibitors
Catalytic agent:

These are the catalytically active component in the catalyst. These components generate
the active sites that participate in the chemical reaction. Activity of any catalyst is
proportional to the concentration of these active sites. Though concentration of the active
sites depends on the amount of catalytically active component, however, it is not always
directly proportional. Availability of active sites depends mainly on the dispersion of
catalytic agent. The dispersion is defined as ratio of total number of exposed
atoms/molecules of catalytic agent available for reaction to total number of
atoms/molecules of catalytic agent present in the catalyst sample.

Catalytic agents may be broadly divided in the following categories:

i. Metallic conductors ( e.g Fe, Pt, Ag, etc.)


ii. Semiconductors (e.g. NiO, ZnO,etc.)
iii. Insulators (e.g. Al2O3, SiO2,MgO etc.)
Metallic conductors: The metals that have strong electronic interaction with the
adsorbates are included in this category. The metals are used in various catalytic
reactions such as methanol synthesis, oxidation , hydrogenation and dehydrogenation
processes.

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Examples of metal catalysts :

Cu for water gas shift reaction and methanol synthesis ; Ag for oxidation of ethylene to
ethylene oxide, Au for oxidation of methanol to formaldehyde; Fe for ammonia
synthesis; Pd and Pt for hydrogenation of olefins, dienes, aniline or nitriles as well as
dehydrogenation of alkanes, alcohols, cyclohexanes, cyclohexanols etc.

Semiconductors :

The oxides and sulfides of transition metals that have catalytic activity are included in
this category. Similar to conducting metals, they are also capable of electronic interaction
with adsorbed species and catalyze the same type of reactions. Usually the lower valence
band electrons participate in bonding. The upper conduction band separated by band gap
energy is empty unless electrons are promoted by heat or radiation. Semiconductor
characteristics may be intrinsic or induced by addition of foreign ion, creating cationic or
anionic vacancies. Common transition oxides and sulfides such as CuO, AgO, NiO CoO,
Fe2O3 , MnO, Cr2O3, FeS, V2O5 show conductivity. These materials participate in
catalytic reactions and reaction occurs through acceptation or donation of electrons
between the reactant material and catalysts. Few applications of semiconductor catalysts
are : CuO for oxidation of nitric oxides, NiO for dehydrogenation of alkanes, MnO2 for
oxidation of alcohols, and V2O5 for oxidation of hydrocarbons.

Insulators : Catalytic functions of insulators are different from that of conductor and
semi conductor materials. Insulators have large values of band gap energy and very low
concentration of impurity levels. The electrons remain localized in valence bonds and
redox type reactions involving electronic interaction as observed for metal or
semiconductor catalysts does not occur. However, insulators have sites that generate
protons, thereby, promote carbonium ion based reactions such as cracking, isomerization
or polymerization. Al2O3, SiO2, SiO2-Al2O3, zeolites, MgO, CaO, MgAl2O4, SiO-MgO
are few examples of the insulators used as catalysts.

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Support or carrier

Support or carrier provides large surface area for dispersion of small amount of
catalytically active agent. This is particularly important when expensive metals, such as
platinum, ruthenium, palladium or silver are used as the active agent. Supports give the
catalysts its physical form, texture, mechanical resistance and certain activity particularly
for bifunctional catalysts. Area of the support can range from 1 - 1000 m2/gm. Common
supports are alumina, silica, silica-alumina, molecular sieves etc. The surface area of α -
alumina is in the range 1-10 m2/gm whereas the surface area for γ or η - alumina can be
in the range 100 – 300 m2/gm.

Support may be inert or interact with the active component. This interaction may result in
change in surface structure of the active agent and thereby affect the catalyst activity and
selectivity. The support may also exhibit ability to adsorb reactant and contribute to the
reaction process.

Promoters :

Promoters are generally defined as substances added during preparation of catalysts that
improve the activity or selectivity or stabilize the catalytic agents. The promoter is
present in a small amount and by itself has little or no activity.

Promoters are termed as physical or chemical promoter depending on the manner they
improve the catalyst performance.

The additives that maintain physical integrity of the support and/or deposited catalytic
agents are termed as physical promoters. For example, addition of small quantities of
alumina to an iron catalyst employed in ammonia synthesis prevents sintering of the iron
crystallites. Thus, for this catalyst, alumina is a physical promoter. The addition of K2O
to the same catalyst increases the intrinsic activity of the iron crystallites and therefore
acts as a chemical promoter. The promoter can be added during catalyst preparation or
during reaction.

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Negative promoters or inhibitors: Inhibitors act opposite to promoters. When added in


small amounts, these can reduce catalyst activity, selectivity or stability. Inhibitor is
particularly useful for reducing the activity of a catalyst for undesirable side reactions. In
oxidation of ethylene, ethylene dichloride is added to inhibit CO2 formation thus acting as
an inhibitor.

Industrial catalysts
Industrial catalysts can be broadly grouped into three categories:

1. Bulk catalysts : When the entire catalyst consists of the catalytically active
substance ,then the solid catalyst is called a bulk catalyst. Examples include silica-
alumina catalysts for catalytic cracking; iron- molybdate for oxidation of methanol
to formaldehyde; iron doped with alumina and potassium oxide for the synthesis of
ammonia.
2. Supported catalysts: In supported catalysts, the catalytically active materials are
dispersed over the high surface area support material. For example,
hydrodesulphurization is carried out over molybdenum oxide supported on
alumina.
3. Mixed agglomerates : These catalysts are agglomerated mixture of active substance
and support. These type of catalysts are used less frequently.

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Precipitation or gel formation from starting materials

Decantation/ filtration

Washing

Drying

Crushing & grinding

Forming

Calcination

Impregnation

Final Activation

Fig. 1. Basic unit operations in solid catalyst preparation

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Preparation of solid catalyst


The catalyst preparation methods can broadly categorized as follows :

1. Bulk preparation process:


Bulk catalysts and supports are prepared by this method. Bulk preparation is
mainly done by the following methods :

a. Precipitation process
b. Sol gel process
2. Impregnation process:
Supports are first prepared by bulk preparation methods and then impregnated with
the catalytically active material. The active materials can be deposited on the
supports by various methods. Most of the methods involve aqueous solutions and
liquid solid interface. In some cases, deposition is done from the gas phase and
involves gas- solid interface.

3. Physical mixing :
Mixed agglomerated catalysts are prepared by this method. These catalysts are
prepared by physically mixing the active substances with a powdered support or
precursors of support in ball mill. The final mixture is then agglomerated and
activated.

Basic unit operations involved in preparation of solid catalyst is shown in Fig 1. Each
step is discussed in detail in the following sections.

Book References :

• J.J. Carberry , Chemical and catalytic reaction engineering, Dover Publications,


2001
• G. Ertl, H. Knozinger & J. Weitkamp, Handbook of Heterogeneous Catalysis, Vol
1, Wiley – VCH, 1997
• R. J. Farrauto & C. H. Bartholomew, Fundamentals of Industrial Catalytic Processes,
Blackie Academic & Professional, 1997
• J.T. Richardson, Principle of catalysts development, Plenum Press, 1989

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Lecture 6

Precipitation and co-precipitation

In this process, the desired component is precipitated from the solution. Co precipitation
is used for simultaneous precipitation of more than one component. Catalysts based on
more than one component can be prepared easily by co-precipitation. The precipitation
process is used for preparation of bulk catalysts and support material such as Al2O3, SiO2,
TiO2, ZrO2 etc.

Process

In general, the metal hydroxides are precipitated from their precursor salt solution
because of their low solubility. The precipitation of hydroxides can be performed either
by starting from an alkaline solution which is acidified or from acidic solution by raising
the pH. However, most hydroxides for technical application are precipitated from an
acidic solution by the addition of an alkaline precipitating agent. Usually, ammonia or
sodium bicarbonate is used as the precipitating agent. Highly soluble inorganic salts such
as nitrates, carbonates or chlorides are generally used as metal precursors. For example,
preparation of alumina is done by precipitating aluminium hydroxide from aluminium
nitrate solution by addition of ammonium hydroxide.

Al ( NO3 )3   +  NH 4 OH  → Al(OH)3 ↓ + NH 4 NO3

During precipitation, several processes occur and the major steps are :

1. liquid mixing / supersaturation


2. nucleation
3. crystal growth to form primary products
4. aggregation of the primary particles

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Initial mixing or interdispersing of components in the solution has a significant effect on


the precipitation. Good mixing result in a more homogeneous product particularly in case
of co- precipitation. Rate of stirring primarily affects the nucleation whereas growth rate
is much less influenced by this factor. Stirring rate also affect the aggregation. Aggregate
size can be influenced by changing the stirring rate and the manner of mixing.

Fig 1. Parameters affecting supersaturation

For nucleation to occur the solution must be super saturated with respect to the
components which is to be precipitated. Parameters affecting supersaturation is shown in
Fig. 1. In supersaturated region the system is unstable and precipitation occurs with any
small disturbance. The supersaturaton region is approached either by increasing the
concentration through evaporation, lowering the temperature or by increasing pH. The
solubility of a component increases with temperature as shown in Fig. 1. The solubility
curve is also function of pH. As pH increases solubility decrease and curve shift from 1
to position 2. Then the point which was initially in solution region becomes in
supersatured region. The increase in pH is the most convenient method for precipitation.
The reaction during precipitation, M n + + nOH −  M(OH)n , is controlled by increasing the
pH through addition of a basic solution. Hence by raising the pH value of a solution by
addition of alkaline or ammonium hydroxide the corresponding metallic hydroxide
compounds can be made insoluble and precipitated from solution. Commonly used

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reagents are NaOH, KOH, NH4OH, carbonates and bicarbonates. Particles within
supersaturated region develop in two steps : nucleation and growth.

Nucleation may proceed spontaneously through the formation of M(OH)n entities or be


initiated with seed materials such as dust , particle fragments, roughness of vessels
surface. Addition of seed material enhances rate of nucleation. The nucleus is defined as
the smallest solid phase aggregate of atoms, molecule or ions which is formed during
precipitation and which is capable of spontaneous growth. In super saturated solution
when the concentration exceeds a critical threshold value, a nucleus will form and the
precipitation will begin. As long as the concentration of the species stays above the
nucleation threshold, new particles are formed. Nucleation starts with the formation of
clusters which are capable of spontaneous growth by the subsequent addition of
monomers until a critical size is reached. Clusters, smaller than the critical size, tend to
re–dissolve, while larger clusters continue to grow. As soon as the concentration falls
below the critical concentration due to consumption of the precursors by nucleation or by
the growth process, only growth of existing particles continues. Growth proceed through
adsorption of ions on surface of seeded particle. This growth is a function of
concentration, temperature and pH. Rates of nucleation and growth can be independently
controlled. If nucleation is faster than growth, the system produces a narrow distribution
of small particles. Fast growth results in narrow distribution of large particles.

Several equations are proposed for nucleation rate and the most commonly used is :

dN  −16πσ 3ν 2 
= β exp  
 3 ( kT ) ln s 
3 2
dt

where β is the pre-exponential term, σ is solid –fluid interfacial energy, υ is solid


molecular volume and T is the temperature. The super saturation ‘s’ is defined as the ratio
actual concentration
of actual concentration to solubility; s =
solubility

dN  −A  16πσ 3ν 2
The equation can be simplified as = β exp  2  A=
 ln s  3 ( kT )
3
dt

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Thus, nucleation strongly depends on the concentration as well as temperature. There is a


critical super saturation concentration below which nucleation is very slow and above
which nucleation is very fast.

There are several mechanisms of crystal growth and most of these lead to the simple

G k ( c − ceq ) , where ‘k’ is the kinetic coefficient, ‘c’ is the


n
equation of growth rate, =

actual concentration and ‘ceq’ is the equilibrium concentration. The value of exponent
‘n’ lies in the range of 1 to 2 and often close to 1.

Hence, the dependency of the crystallite growth rate on concentration is closer to a linear
function while nucleation rate increases exponentially with concentration. Therefore,
high super-saturation level promotes nucleation rather than crystal growth and favor the
precipitation of highly dispersed materials. In contrast, precipitation from a more dilute
solution tends to produce fewer but larger crystals.

Apart from nucleation and crystal growth, aggregation is also an important step.
Aggregation leads to fewer and larger but yet porous particles. It is the formation of
clusters of nano-scale primary particles into micrometer scale secondary particles.
Physical and chemical forces can hold these particles together. Porosity is then
determined by how the particles are stacked and the pores are considered as void spaces
between the primary particles. Because of very high super-saturation during the
precipitation of most base metal hydroxides or carbonates , nucleation is spontaneous.

Process variation

Precipitation process can be carried out in different ways. The process can be carried out
either in batch mode or in continuous mode. The other process variation that affects the
precipitate properties is the sequence of addition of the starting materials.

In a batch process, the salt solution from which the metal hydroxide is to be
precipitated is taken in a vessel and the precipitating agent is added. The advantage of
this method is its simplicity. However, variation of batch composition during
precipitation process is a major limitation. This can lead to differences in the properties
of the precipitate formed in the initial and final stages. The continuous process involves

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continual simultaneous addition of salt solution and precipitating agent to a vessel with
simultaneous withdrawal of precipitate. This process has a higher demand on process
control. All the parameters (pH, temperature, concentration, residence time) can be
controlled as desired.

The order of addition of starting materials also affects the final properties of the
precipitated catalysts. Different schemes of addition of starting materials in precipitation
process is shown in Fig. 2.When metal solution is added to the precipitating agent, the
product tends to be homogeneous since the precipitating agent is present in large excess.
This process is particularly important in co-precipitation as it give more homogeneous
product than the process where the precipitating agent is added to a mixed metal solution.
In the latter case, the hydroxide with lower solubility tends to precipitate first, resulting in
formation of non-homogeneous product. Simultaneous addition of both reagents to a
buffer solution of constant pH results in better homogeneity and process control. In this
process, ratio of metal salt and precipitating agent can be controlled. However, product at
the start and at the end may vary due to change in concentration of other ions that are not
precipitated. These counter ions tend to occlude in larger extent in final products. Aging
is also longer for final products. Aging represent time of formation of coprecipitated and
its separation from solution. Aging results in change in structure and properties of
hydroxide network. Aging leads to more crosslinked network.

Buffer solution

Fig. 2. Different schemes of addition of starting materials in precipitation process

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Advantages and disadvantages: The main advantage of the precipitation process is the
possibility of creating pure and homogenous material. However, the major disadvantages
include necessity of product separation after precipitation and generation of the large
volume of salt containing solutions. There is also difficulty in maintaining a constant
product quality throughout the whole precipitation process if the precipitation is carried
out discontinuously.

Process parameters

In addition to the process variations discussed above there are many other parameters that
affect the final product properties as shown in Fig.3. The properties of the final product
that are affected include phase formation, chemical composition, purity, particle size,
surface area, pore size and pore volume. It is necessary to optimize the parameters to
produce the desired product.

Temperature pH

Precipitate properties
Raw materials Solvent
(phase, composition, purity,
particle size, surface area,
Additives pore size Composition

Concentration

Fig. 3. Parameters affecting the properties of the precipitate

Effect of raw materials : The precursors are usually chosen with counter ions that can
easily be decomposed to volatile products during heat treatment steps. Nitrates and
carbonate salts are preferably used as metal precursors whereas ammonia or sodium
carbonate as the precipitating agent. Chloride and sulphate ions act as poisons in many
catalytic processes. Such ions should be avoided in the precipitation process. However, if
the precipitation is needed to be carried out in the presence of these ions then repeated
washing steps are necessary to remove these ions from the precipitate.

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The nature of the counter ions present in the solution can also influence particle
morphology, particle size and phase distribution. It has been observed that preparation of
MoO3 from Na2MoO4 precursor salt results in small particles with relatively high surface
area whereas use of (NH4)6Mo7O24 as precursor salt results in larger particles.

Effect of pH : pH directly control the degree of super saturation and hence is expected
to affect the final properties. But the influence of pH is not simple and has to be
investigated experimentally for the specific system. In aluminium oxide system, the
precipitation pH is one of the parameters that determines the phase formation. In general,
it has been found that precipitation in alkaline medium (pH > 8) leads to the formation of
bayerite (β-Al(OH)3), while precipitation in more acidic conditions favors formation of
boehmite (γ-AlO(OH)).

Effect of concentration and composition: It is desirable to precipitate at high


concentration levels of metal ions. This increases the space time yields by decreasing the
vessel volume for the same mass of precipitate. Moreover, higher degree of super-
saturation leads to faster precipitation. Higher concentration levels also results in smaller
particle size and higher surface areas due to increased nucleation rates.

If the catalysts are prepared by co-precipitation, the composition of solution determines


the composition of the final product. Deviation from solution composition generally
occurs if the solubilities of the different components differ significantly and the
precipitation is not complete. The precipitation can be carried out simultaneously or
sequentially. When the solubility of the components is not too different, then the
precipitation will occur almost simultaneously. However, if the solubility of the
components differs significantly then the component with lower solubility will
preferentially precipitate resulting in sequential precipitation.

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Effect of solvent : For preparation of bulk catalysts and supports, water is almost
exclusively used as the solvent for economic reason. Organic solvents are much more
expensive to use. Furthermore, solubilities of most metal salts used as the precursors are
lower in organic solvents. Organic solvents are also environmentally hazardous. So use of
organic solvents is very limited. These are used only in specific cases where product
quality obtained is better by using organic solvent.

Effect of temperature : The precipitation temperature is a decisive factor in controlling


precipitate properties such as primary crystallite size , surface area and the phase formed.
Till date it is very difficult to predict the exact nature and extent of effect of the
precipitation temperature on the properties and is generally determined experimentally.
Nucleation rates are extremely sensitive to temperature. In general, most precipitation
processes are carried out above room temperature , often close to 373 K for obvious
reason that the precipitation is more rapid. A higher temperature may result in an
increase in crystallite size, though this depends on the kinetics of different elementary
processes. Sometimes, no effect of temperature or even lowering of size of the crystallites
is observed as in the case of ZnO system. Temperature also affects the phase formation.
During preparation of Ni/SiO2 catalysts, at high temperatures nickel hydro-silicate is
obtained while at lower temperatures, the main precipitate is nickel hydroxide.

When use of high temperature is detrimental, the rotary evaporator is often used to
remove the solvent from slurry solution. Rotary evaporator is a vacuum evaporator in
which pressure is lowered above the slurry so that boiling point of the solvent is reduced
and it can be removed without using excessive heating. In the evaporator a rotating
evaporating flask is connected to vapor duct to draw off the vapor and thereby, reduce the
pressure within evaporator system. Sample solution is gently heated in bath, usually
water bath, to enhance the solvent removal. The separated solvent vapor can be
condensed back using a condenser and collected in a separate flask.

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Effect of Additives : Additives are substances which are not necessary ingredients of a
precipitation reaction. The properties of the precipitates can strongly be influenced by
additives. The most widely used additives are organic molecules which are added to the
precipitate in order to control the pore structure. Such organic molecules can later be
removed from the precipitate in the calcination step.

A very promising route for the preparation of the high surface area oxides is the use of
surfactants as additives. Removal of the surfactant by calcination steps leaves a well-
defined pore network. The pore diameter can be adjusted in the range of 2-10 nm. These
all are treated as trade secrets and details are not available in the public domain.

Preparation of dual oxides catalysts by coprecipitation

Mixed oxide support and catalyst can be prepared by coprecipitation method. As


discussed earlier, for coprecipitation, the solubility of the two components should be in
similar range for simultaneous precipitation resulting in homogeneous product. Otherwise
the precipitation will be sequential resulting in non-homogeneous product.

Two examples are discussed below.

1. SiO2-Al2O3

SiO2-Al2O3 is used in catalytic cracking process and is also used as support for active
metals in various applications. Preparation of dual oxides by coprecipitation is similar to
precipitation of single oxide. At pH 6 (at 50 0C) the precipitation of both silica and
alumina sols begins and gelation takes places.

2. NiO-Al2O3

NiO-Al2O3 is used for hydrogenation and methanation reactions. Although this catalyst
can be produced by other route, coprecipitation method of preparation is also done to
increase the intimate interaction between active metal and support. The sodium
bicarbonate can be used as precipitating agent for formation of nickel aluminium
hydroxyl carbonate with good homogeneity of final product.

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Book References :

• K.P. de Jong. , Synthesis of solid catalysts , Wiley –VCH, 2009


• J.T. Richardson, Principle of catalysts development, Plenum Press, 1989
• G. Ertl, H. Knozinger & J. Weitkamp, Handbook of Heterogeneous Catalysis Vol 1,
Wiley – VCH, 1997
• R. J. Farrauto & C. H. Bartholomew, Fundamentals of Industrial Catalytic Processes,
Blackie Academic & Professional, 1997
• S. P. S. Andrew, Chemical Engineering Science 36 (1981) 1431-1445

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Lecture 7

Sol gel method

In the sol gel process, initially a stable colloidal solution called sol is formed. The sol is a
liquid suspension of solid particles ranging in size from 1 nm to 1 micron. It can be
obtained by hydrolysis and partial condensation of precursors such as an inorganic salt or
a metal alkoxide. The further condensation of sol particles into a three dimensional
network produces a gel material. The gel is a diphasic material in which the solids
encapsulate the solvent. The molecular weight of the oxide species produced
continuously increases. The materials are referred to as aqua sol or aqua gels when water
is used as a solvent and aquosol or alcogel when alcohol is used. The general scheme of
preparation by sol gel method is shown in Fig. 1

The encapsulated liquid can be removed from a gel by either evaporative drying or with
supercritical drying /extraction. The resulting solid products are known as xerogel and
aerogel, respectively. When gels are dried by evaporation, the dried product is called
xerogel. When the gels are dried by supercritical drying, the dried gel is called aerogels.
The aerogel retains high porosity and has very high pore volume.

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Sol

Xerogel Aerogel

Fig. 1. General scheme of preparation by sol gel method

The sol gel method is distinguished from other routes of material preparation from
solutions or melts such as precipitation and crystallization by two main characteristics:

1. Formation of clear colloidal solution due to primary condensation of dissolved


molecular precursors.
2. These colloidal particles merge during subsequent gelation stage into polymeric
chains by chemical bonding between local reactive groups at their surface.

Both stages are controlled by condensation chemistry that can include as a first step,
hydrolysis of hydrated metal ions or metal alkoxides molecules. The condensation
chemistry in this case is based on olation/oxolation reactions between hydroxylated
species. Olation is a condensation process in which a hydroxyl bridge “–OH--” bridge is
formed between two metal centers.

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The oxolation is a condensation reaction in which an oxo bridge “-O-” is formed between
two metal centers. The steps in sol gel processing are shown in Fig. 2 and discussed
below.

Activation and polycondensation : Metal alkoxides are used as precursors in sol-gel


operation. Metal alkoxides are most extensively used as these are commercially available
in high purity and their solution chemistry is well documented. For preparation of
alumina and zirconia, aluminium propoxide and zirconium propoxide are used
respectively as precursors.

The metal alkoxides are hydrolysed in alcohol solution containing a controlled amount of
water. The sol gel chemistry can be represented by following two reactions :

Hydrolysis:   
→ -MOH  + ROH      
-M-OR + H 2 O    
Condensation: →
-M-OH +  XO-M-      -M-O-M-  +  XOH    

Where M= metal ; X = H or R (alkyl group)

This is a very simplified representation without giving details of the intermediate or end
products. However, this gives an idea of the formation of three dimensional gel network
coming from the condensation of partially hydrolyzed species.

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Conversion (activation) of molecular precursor to the reactive state

Polycondensation of activated molecular precursor to nanocluster forming sol

Gelation

Aging

Washing

Drying process

Heat treatment

Fig. 2. Basic steps in sol gel processing

Parameters affecting any of the two reactions will affect the properties of the final
product. Two of the main parameters that affect are (1) amount and rate of water
addition and (2) pH of the solution. The amount of water added is expressed in terms of
hydrolysis ratio ‘h’ and defined as

moles of water
h=
moles of metal alkoxide M(OR) m

When h < 1, there is less possibility of forming infinite network because of the presence
of few M-OH groups for cross linking and gelation. If excess amount of water is
present, that is h>m, extensively cross linked gel can be formed. For a given amount of
water, another way to control the process is to control the rate of addition of water.

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The pH of the system affects the relative rate of hydrolysis and condensation. Fig. 3
compares the rates of hydrolysis and condensation of tetra ethyl ortho silicate (TEOS), a
very widely used precursors , as a function of pH. Under acidic conditions, hydrolysis
occurs at a faster rate than condensation and the resulting gel is weakly branched. Under
basic conditions, the reverse occurs and the resulting gel is highly branched and contains
colloidal aggregates. Subsequently, dried and heat treated samples have different surface
functions and pore structures.
The image part with relationship ID rId28 was not found in the file.

Fig. 3. Effect of relative rates of hydrolysis and condensation reactions on gel structure.

Gelation : After a period of time the sol experiences a transition from liquid solution to a
cross-linked gel state where it can support an elastic stress. This period of time is known
as gel time or gelation time, and during this time the viscosity of the solution undergoes a
rapid increase corresponding to the transition from a viscous fluid to an elastic gel. At the
end of gelation there is a continuous phase containing a structure that reflects formation
and branching of particles under specific growth conditions. The formation of a network
results in entrapping of the solution. The gel structure is determined by the ionic
character of the M-O bond and the relationship between the hydrolysis and condensation
rate.

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The image part with relationship ID rId29 was not found in the file.

Fig. 4. Double layer structure for particles

Effect of zeta potential on gelation: The particle surface may be positively or negatively
charged depending on the pH. With an acidic solution, that is low pH, the equilibrium is
driven towards positive surfaces. As pH increases, the surfaces become less positively
charged and finally negatively charged. However, the effective charge on the surface is
partially neutralized by the counter- ions in the solution that may originate from the bases
used during precipitation or electrolytes added during aging. Theses counter- ions form a
space charge, part of which is held sufficiently strongly to be carried along as the
particles move with Brownian motion (Fig. 4). The result is an effective charge called
Zeta potential. Both the original charge and the neutralizing counter- ions respond to pH
changes. This zeta potential determines the rate of gelation. If the charge is high,
particles effectively repel one another and avoid contact. If it is low, then thermal motion
leads to collision and coalescence. These rates are highest at the isoelectric point where
the zeta potential is zero. The variation of zetapotential with pH for alumina is shown in
Fig. 5.

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The image part with relationship ID rId30 was not found in the file.

Fig. 5. Effect of pH on zeta potential of alumina

Two other important parameters are temperature and solvent. Varying temperature is
most effective when it can alter the relative rate of the competing reactions. Solvent can
change the nature of an alkoxide through solvent exchange or affect the condensation
reaction directly.

Aging : After visible formation of gel, processing proceeds to the aging step where the
structure and the properties of the formed network continue to change up to the point that
yields the target density. It represents the time between the formation of the gel and the
removal of solvent. As long as the pore liquid remains in the matrix, a gel is not static and
can undergo many transformations. This step includes four processes : polycondensation
, syneresis, coarsening , and phase transformation.

Polycondensation between surface functional groups continues to occur after the gel
point. This process is actually desirable as it leads to a more cross-linked network that is
mechanically stronger and consequently easier to handle. However, extensive
condensation can lead to shrinking of the gel to such an extent that the solvent is actually
expelled in a phenomenon called syneresis. Parameters that affect this process include
temperature, time, and pH of the pore liquid. However, studies off theses effects are still
very qualitative.

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A typical preparation of zirconia aerogel is shown in Fig. 6. Zirconium propoxide is used


as precursor for zirconium. The sol prepared from precursor solution is aged for 2h and
then supercritically dried. In this example calcination is done in two steps.
The image part with relationship ID rId31 was not found in the file.

Fig. 6. Sol gel parameters in preparation of zirconia aerogels

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Book References :

• K.P. de Jong. , Synthesis of solid catalysts , Wiley –VCH, 2009


• J.T. Richardson, Principle of catalysts development, Plenum Press, 1989
• G. Ertl, H. Knozinger & J. Weitkamp, Handbook of Heterogeneous Catalysis Vol 1,
Wiley – VCH, 1997
• R. J. Farrauto & C. H. Bartholomew, Fundamentals of Industrial Catalytic Processes,
Blackie Academic & Professional, 1997

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Lecture 8

Supported catalysts
Supported catalysts are prepared by deposition of the active metal on the support
materials. The main purpose of using a support is to achieve an optimal dispersion of the
catalytically active component and to stabilize it against sintering. But in many reactions
the support is not inert and the overall process consists of two catalytic functions both for
active components and support.

Supported catalysts are prepared in two main steps:

1. Deposition of the precursor of the active component on the support.


2. Transformation of this deposited precursor to catalytically active site.
The final active component can be in metallic state, oxide form or reduced from
depending on the requirements.

There are various deposition methods. Most of these involve aqueous solutions and liquid
solid interface. In some cases, deposition is also done from the gas phase and involves
gas- solid interface. The methods most frequently used are:

a. impregnation
b. ion exchange
Impregnation
Impregnation can be classified in two categories according to the volume of solution
used.

Dry or incipient impregnation

In this method, a previously dried support is contacted with volume of solution equal to
its pore volume. The solution contains the required amount of the precursors of the active
phase. As soon as the support is placed in contact with the solution, the solution is drawn
into the pores by capillary suction. In case of proper wetting, no excess solution remains
outside the pore space. Part of the air present in the pores is imprisoned and compressed
under the effect of capillary forces. The pressure developed inside the imprisoned gas

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bubbles depends on the radius, r, of the curve of the liquid -gas meniscus and may reach

several MPa when r < 100 nm as a result of Young - Laplace law,  P = P − P ' = ,
r
where γ is the liquid- gas interfacial tension. Considerable forces will thus be exerted on
the portions of the pore walls in contact with these bubbles. The walls that are not strong
enough may break down causing a degradation of the mechanical properties.
Occasionally, even bursting of the catalyst grains occurs. However, the development of
the high pressure is a transitory phenomenon. Under highly compressed conditions, air
dissolves and progressively escapes from the solid.

Wet / diffusional impregnation

In this method, the pore space of the support is first filled with the same solvent as used
in the impregnating precursor solution. The wetted support is then treated with the
impregnating precursor solution. Here the actual impregnation takes place in diffusional
condition when solvent filled support is dipped in the precursor solution.

The first phase of saturation of the support by solvent involves the characteristics of dry
impregnation. But in the second phase, when solvent saturated support is added to the
impregnating solution, high pressure is not developed within the pores. The precursor salt
migrates progressively from the solution into the pores of the support. The driving force
at all times is the concentration gradient between the bulk solution and the solution within
the pores. The impregnation time is much longer than for dry impregnation.

Wet impregnation should be avoided when the interaction between the precursors and the
support is too weak to guarantee the deposition of the former.

Mechanism of impregnation: The mechanism of wet impregnation is simpler compared


to dry impregnation. In wet impregnation, the distribution of the solute inside the pores is
assumed to be governed by two phenomena (Fig 1):

1. Diffusion of the solutes within the pores. It is described by Fick’s law


2. Adsorption of the solute onto the support. This depends on the adsorption capacity
of the surface and on the adsorption equilibrium constant.

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The distribution of the precursors within the pellets depends on the balance between these
diffusion and adsorption phenomena.

(a) Wet impregnation (b) Dry impregnation

Fig. 1. Schematic representation of basic processes involved during impregnation of precursors on porous support.

In case of dry impregnation, in addition to diffusion and adsorption processes, another


phenomenon occurs, which is the pressure driven capillary flow of the solution inside the
empty pores. This can be represented by Darcy’s law. An important parameter from
introduction of Darcy law is the solution viscosity ‘μ’. In case of aqueous solution and in
the common range of concentration used for impregnation, viscosity increases almost
proportionally with concentration. It also increases with the presence of organic ligands
attached to the metal ions. Viscosity and concentration have opposite effects on
precursor diffusion; a high concentration tends to favor the diffusion of the solute
towards the centre of the pellet, while a high viscosity tends to hinder the diffusion.

Drying

Impregnation is followed by elimination of the solvent. The impregnated sample is


heated in an oven in a flow of gas, as discussed earlier. The gas may be air, oxygen,
nitrogen or any other gas depending on the requirement. The temperature is generally
maintained slightly higher than the boiling point of the solvent e.g 110-120 0C for water.
The elimination of water from the pores leads to the increase of precursor concentration

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up to saturation and consequent crystallization, preferably on the seeds resulting from the
interaction with the support. Apart from temperature, heating rate affects the drying
process.

(a) Constant rate period of drying (b) Falling rate period of


drying

Fig. 2. Schematic representation of drying process during impregnation method

Drying Mechanism: The drying process can be modeled considering the outward
convective flow of liquid towards the pore mouth at pellet surface where the solvent
evaporation occurs. This convective flow can be described by Darcy’s law and is
associated with the outward flow of the precursors that is favored by a low viscosity of
the solution. As the precursor concentration increases near the outer surface of the pellet
due to this outward flow, an inward back diffusion of precursors, which can be modeled
by Ficks law, takes place. Apart from these two flows in opposite directions, another
factor that needs to be considered is the interaction between the precursor and support
surface. Schematic representation of drying process during impregnation method is
shown in Fig. 2.

The distribution of the precursor phase in the pellet or its segregation at the outer surface
depends on the relative contribution of adsorption, convection and back-diffusion as long
as the flow of solvent is high. This corresponds to constant rate period of drying.

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As the solvents recedes inside the pores, evaporation occurs within the pores
corresponding to the falling rate period. The drying regime is defined as slow if the
constant rate period predominates and as fast if it is falling- rate period controlled.

Precursor distribution: The distribution of precursors within the pores of support


depends on various factors. The different conditions of impregnation and drying can
result in broadly three types of precursor distribution as described in Table 1. In Egg
shell type distribution the precursors are preferentially accumulated near the pore wall.
This type of distribution is obtained if during impregnation precursors are strongly
adsorbed on the pore wall. High viscosity of the solution also tends to result in egg shell
distribution. For slow drying, egg shell distribution can result even in low viscosity and
weak adsorption conditions. In egg yolk type distribution the precursors are accumulated
in the interior core of the pores. Egg yolk distribution is obtained if during impregnation,
the competing ions are present that have stronger interaction with the pore wall of
supports. Fast drying regime with predominant back diffusion also results in egg yolk
distribution. In uniform precursor distribution, precursors are uniformly distributed across
the pores. If the adsorption of the solutes is weak and the time is long enough,
distribution tends to be uniform. Uniform distribution also results when precursors and
competitors interact equally with the surface or the impregnating solution is concentrated
and viscous. Room temperature drying with weakly adsorbing precursors also tends to
give uniform precursor distribution. For powders, the equilibrium is reached within few
minutes. However, in case of pellets it may take up to several hours to reach a uniform
distribution of the precursors.

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Table 1. Distribution of precursor at different conditions of impregnation and drying.

Precursor Conditions of Impregnation and drying


distribution

Egg shell distribution 1. Strong adsorption of precursors during impregnation


2. High viscosity of impregnating solution
3. Slow drying regime for low concentration, low viscosity
and weak adsorption conditions

Egg yolk distribution 1. In presence of competitor ions that have stronger


interaction with the supports
2. Fast drying regime with predominant back diffusion

Uniform distribution 1. Precursors and competitors interact equally with the


surface.
2. Impregnating solution is concentrated and viscous
3. Room temperature drying with weakly adsorbing
precursors

Parameters affecting the impregnation process

The pH of the solution is an important parameter in the impregnation process. On liquid


side, pH determines the most abundant species in solution to be deposited on to the
support. HNO3, carboxylic acids, ammonia are usually used for adjusting the pH because
these can decompose during thermal treatment. On solid side, pH controls the nature of
surface charge and the number of charged sites, in other words, the zeta potential. During
impregnation, the extent of interaction between the metal complex and the support is
controlled by parameters such as isoelectric point of oxide support, temperature and
nature of support and dopants.

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Ion exchange

Ion exchange consists of replacing an ionic species by another ionic species in


electrostatic interaction of the precursors with the surface of a support. The support
containing the ion A is dipped into an excess volume (compared to the pore volume) of a
solution containing ion B that is to be introduced. Ion B gradually penetrates into the pore
space of the support and takes the place of ion A, which passes into the solution. This
continues until equilibrium is established corresponding to a given distribution of the two
ions between the solid and solution.

Natural ion exchangers: Natural exchangers are composed of a frame work having
charge that is neutralized by ions of opposite charge. For example, zeolite has negatively
charged framework due to the particular environment of aluminium. Aluminium, just like
silicon, is effectively situated in the centre of a tetrahedron of four oxygen atoms which
have four negative charges, where as aluminium has only three positive charges. The
tetrahedron (AlO4) thus have an overall one negative charge distributed over the oxygen
atoms and this charge is neutralized by the presence of various cations such as Na+, K+
etc. These cations are not definitively bonded to the framework but may be replaced by
other cations during an ion exchange operation. Zeolite has a constant number of these
exchange sites which are equal to the number of aluminium atoms in their framework.
Clays, silicates are also cation exchangers.

Mechanism of single ion exchange: Single ion exchange takes place when in the solid-
solution system only two ions interact. If ion A+ on the solid Z is to be replaced by ion B+
present in the solution then in the simple case of two monovalent cations, the exchange

equilibrium can be written as  Bz+ + As+


Az+ + Bs+ 

The subscripts ‘s’ and ‘z’ represent solution and solid, respectively. In case of ideal
exchange, that is both the exchanger and solution are ideal with single type of adsorption
sites, the equilibrium constant Ka can be written as

CBZ C AS
Ka 
CBS C AZ

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C AZ = concentration of ion A + in the solid


C AS = concentration of ion A + in the solution
CBZ = concentration of ion B+ in the solid
CBS = concentration of ion B+ in the solution

C AZ + CBZ =
CZ = total concentration of cations in the solid
C AS + CBS =
CS = total concentration of cations in the solution

Therefore it follows that

K a CZ CBS
CBZ =
CS ( K a − 1) CBS

If it is not an ideal system, the above equation must be expressed in terms of


concentration and activity coefficients.

Example: Na+ ions in NaY zeolites can be replaced by NH4+ ions. NaY zeolite
[Na2O.Al2O3. 5 SiO2] contains 9.9 wt% Na and 73% Na can be exchanged.

Book References :

• K.P. de Jong. , Synthesis of solid catalysts , Wiley –VCH, 2009


• J.T. Richardson, Principle of catalysts development, Plenum Press, 1989
• G. Ertl, H. Knozinger & J. Weitkamp, Handbook of Heterogeneous Catalysis Vol 1,
Wiley – VCH, 1997
• R. J. Farrauto & C. H. Bartholomew, Fundamentals of Industrial Catalytic Processes,
Blackie Academic & Professional, 1997

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Lecture 9

Washing and filtering


Washing can be done by decantation. This method is time consuming. In this method the
precipitate or gel is added to a large volume of distilled water and the suspension is
thoroughly stirred. Then, the suspension is allowed to settle. The foreign undesirable ions
are desorbed from particles as they settle down slowly at the bottom. When a clear
interface is visible, the water is removed by decantation and the process is repeated. The
number of washings required is determined by checking the impurity level of the
decanted water. After washing, the precipitate or gel is filtered. The process can be
reversed. That is the filtration is done first and the precipitate or gel is washed with
distilled water in the subsequent step. This method takes less time. Impurity level in the
wash water is checked to determine the required number of washings.

Drying
Drying is described as the elimination of water or solvent from the pores of the
precipitate or gel. It can be done in two ways:

• Solvent evaporation
• Super critical drying
Solvent evaporation : This type of drying is done in a conventional oven at 100-200 0C
and is generally accompanied by a contraction of the structure. In case of gel, the product
obtained from ordinary drying is known as dry gel or xerogel. Initially, drying occurs
through evaporation of moisture from the outside surface of the materials. The rate of
water loss is constant and the mass transfer is controlled by temperature, relative humidity
and flow rate of air over the surface and the size of the filtrate. The process continues until
the moisture content drops to about 50%. Continued moisture loss occurs with a declining
rate in which evaporation is controlled by capillary forces. The saturation point decreases
as the pore become smaller and the evaporation slows until water is forced into larger pores
by concentration gradient. At the moment of drying, as the pore liquid is evaporated from a
gel network, the capillary pressure associated with the liquid vapor interface within a pore
can become very large for small pores. The capillary pressure that can develop in a pore of

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2γ cos α
radius r is P = , where P is capillary pressure, γ is surface tension, r the pore
r
radius and α is the contact angle between liquid and solid. The capillary pressure with
water evaporating from a pore with a radius of 1 nm is in the order of 1480 atm. Large
capillary tension can lead to collapse of internal structure resulting in loss of pore volume
and surface area. This phenomenon is more significant for a gel having more intricate
porous structure compared to ordinary precipitated material. For a given pore size, the
capillary pressure can be reduced by

1. Using a solvent with a lower surface tension or with a contact angle close to 900.
2. Eliminating the liquid -vapor interface altogether with either supercritical or
freeze drying.
If temperature gradient is high so that evaporation rate is much faster compared to
removal of moisture that is slowed by smaller pores, then large internal pressure of steam
develops and also leads to collapse of structure. Therefore, high temperature gradient in
the sample must be avoided. Drying at a lower temperature gives less surface area loss
since evaporation rates are lower.

Supercritical drying is aimed at eliminating the liquid vapor interface and the
accompanying capillary pressure responsible for structure collapse during conventional
drying particularly for gels. It is used where retention of original microstructure of the
product is important. This process typically involves displacement of water using an
alcohol followed by removal of this alcohol/water mixture using supercritical carbon
dioxide. In this process, the gels are placed in an autoclave filled with ethanol. The
system is pressurized to at least 750-850 psi with CO2 and cooled to 5-10 0C. Liquid CO2
is then flushed through the vessel until all the ethanol has been removed from the vessel
and gels. When the gels are ethanol-free, the vessel is heated to a temperature above the
critical temperature of CO2 (31 0C). As the vessel is heated, the pressure of the system
rises. CO2 is carefully released to maintain a pressure slightly above the critical pressure
of CO2 (1050 psi). The system is held at these conditions for a short time, followed by a
slow, controlled release of CO2 to ambient pressure. As with previous steps, the length of

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time required for this process is dependent on the thickness of the gels. The process may
last anywhere from 12 hours to 6 days.

Calcination or sintering
After the removal of pore liquid, further heat treatment is necessary to convert the
precipitate or dry gel to catalytically useful form. After drying, the next step of heat
treatment is known as calcination. Often the heating is done in the presence of flowing air
or oxygen to burn any residual organics or to oxidize the sample. Multiple changes occur
during this process including:

1. Active phase generation: The hydroxide form is converted to oxide form.

2. Stabilization of mechanical properties: The catalysts sample is subjected to a


more severe heat treatment than that is likely to be encountered in a reactor. This
ensures the stability of its textural and structural properties during reaction.

3. Loss of chemically bound water: The chemically bound water is removed at


higher temperature.

4. Changes in pore size distribution and surface area due to sintering: Exposing the
sample to high temperature over an extended period of time leads to sintering and
consequently decreases the surface area.

5. Change in phase distribution: Higher temperature cause material to crystallize


into different structural forms. Fig. 1 shows the formation of various phases of
alumina when calcined at different temperatures.

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The extent of change in the physical characteristics of the final sample depends on
following parameters: temperature, heating rate, heating time and gaseous environment.

Fig. 1. Formation of various phases of alumina on calcination at different temperatures

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Catalyst shaping and formulation


Mainly, solid catalysts are used in industrial catalytic processes and these are formulated
in different forms such as pellets, extrudates, granules or sphere form.

Formulation and shaping of solid catalysts is done to :

(a) avoid high pressure drop in fixed and moving beds


(b) increase thermal resistance against sintering fracture or phase transition
(c) increase mechanical resistance against crushing and attrition
(d) ensuring high effective heat conductivity in fixed and moving bed for strongly
exothermic and endothermic reactions
Aiming at highest catalyst efficiency is the primary objective in catalyst design because
conversion, selectivity and thermal resistance are strongly affected by the above-
mentioned parameters. Some of the common catalysts formulation techniques are :

a. pellet formation
b. granulation
c. extrusion
d. spray drying
Pellet formation :

It is a high pressure agglomeration technique producing particles of uniform shape and


dimensions. Typically, the dry catalyst powders are compressed in a dye by applying
forces between 50-80 kN with a pending tool. Factors such as ultimate tensile strength of
the materials, moisture content, porosity, stickiness are important. Some materials, such
as kieselguhr, undergo easy pellet formation whereas other materials such as alumina
require addition of small amount of plasticizers or lubricants such as graphite, talc etc.
Important processing parameters are the maximum applied pressure and the rate of
pressure rise. Both influence the hardness of the pellets as well as the integrity of
compacted particles.

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Granulation :

This is a size enlargement process by wet tumbling. In this method, the particles are
tumbled in a cylinder. A cohesive liquid is sprayed onto the catalyst powder such that the
wetted particles stick together. The granules grow by contacting further particles. Product
with wide size distribution can be produced by controlling parameters such as binders
type and concentration, rpm of pan, granulation time and angle of inclination of pan.
Typically, pan granulation yields spherical particles of diameters in the range of 2-20
mm.

Extrusion :

It is a widely used technique. In this method, a suspension or paste of the catalyst powder
is passed through a profiled die that determines the shape of the body. Screw extruders
are very common in use. Slurry of the catalyst is fed to the extrudate at one end and the
screw forces the slurry through the holes at the other end. As the ribbon of slurry emerges
from the holes, a knife is arranged at the end to cut it to the required size. Particles of
narrow size distribution can be obtained by this method.

Spray drying :

This process involves atomization of slurry feedstock into a spray of droplets and
contacting the droplets with hot air in a drying chamber. Particle sizes are determined by
the size of droplets, which is controlled by design of spray nozzles, slurry flow rate,
slurry viscosities. Products in a spray dryer are spheres of diameters in the range of 0.05
to 0.5 mm.

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The schematic diagram of catalyst formulation techniques are shown in Fig. 2.

Cylindrical
vessel

Catalyst slurry feed in Spray


nozzle

Catalyst ribbon

Knife
for
cutting

Fig. 2. Schematic diagram of different catalysts formulation techniques

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Book References :

• K.P. de Jong. , Synthesis of solid catalysts , Wiley –VCH, 2009


• J.T. Richardson, Principle of catalysts development, Plenum Press, 1989
• G. Ertl, H. Knozinger & J. Weitkamp, Handbook of Heterogeneous Catalysis, Vol
1, Wiley – VCH, 1997
• R. J. Farrauto & C. H. Bartholomew, Fundamentals of Industrial Catalytic Processes,
Blackie Academic & Professional, 1997
• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications,
2001

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Lecture 10

Catalyst characterization

Characterization of heterogeneous catalyst refers to the determination of its physical and


chemical characteristics, which are responsible for its performance in a reaction.
Characteristics of catalysts include:

• Chemical composition of the bulk and surface of the solids


• Surface area and porosity ( micro, meso and macro)
• Bulk solid structure, phase composition, crystallite size
• Surface morphology
• Surface chemical properties such as:
o location and oxidation state of active metals
o acid-base property
o reducible – oxidizable property
• Aggregate properties such as aggregate or particle size, density, mechanical
strength and attrition resistance
• Catalytic properties : activity , selectivity, stability

Objectives of characterization

The primary objective of catalyst characterization is to understand the relationship among


physical, chemical and catalytic properties. For this purpose, the physical and chemical
properties are determined by various characterization techniques and related to its activity
and selectivity. This is essential for design and process optimization. The
characterization is also done to monitor the changes in physical and chemical properties
of the catalyst during preparation, activation and reaction stages for better understanding
and quality control. Determination of the extent of deactivation of catalysts during the
reaction process is also important. Characterization of used catalysts can help to
determine the causes of deactivation and minimize it. It also helps to design procedures
for catalysts regeneration.

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Characterization Techniques

In this section some of the characterization techniques that are most commonly used will
be discussed. These techniques are summarized below.

1. Structural analysis
(a) Surface area
• widely accepted BET ( Brunauer, Emmet and Teller) method used for analyzing
multilayer physisorption isotherms of inert gases to determine the surface area
(b) pore analysis by
• BJH method
• mercury intrusion method
(c) X-Ray Diffraction (XRD) :
• can detect crystalline materials having crystal domains greater than 3-5 nm.
• characterization of bulk crystal structure and chemical phase composition.

2. Chemisorption technique
• determines dispersion of metal in catalysts
• determination of surface metal area

3. Thermal analysis
(a) temperature programmed reduction (TPR) :
• measures the rate of reduction of active metals as function of temperature.
• can be correlated with activity of catalysts
(b) temperature programmed desorption (TPD) :
• measurement of rate of desorption of adsorbed molecules as function of
temperature
• mainly used to of study acid –base property of catalysts
(c) Thermo Gravimetric Analysis (TGA) :
• measurement of weight loss (or gain) as a function of temperature in a
controlled gaseous atmosphere;

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• process associated with mass change can be detected and analyzed


(d) Differential Thermal Analysis (DTA)
• monitoring the temperature difference between sample and reference
• process associated with latent heat of transition can be detected and analyzed

4. Spectroscopic techniques
(a) Infra red spectroscopy
• identify compounds and investigate sample composition
• Study of structure and bonds
(b) Raman spectroscopy :
• study of oxidation state and interaction of metal oxides

5. Microscopic technique
(a) Scanning electron microscopy (SEM):
• image the topography of solid surface
• resolution better than 5 nm.

(b) transmission electron microscopy (TEM) :


• determines the micro –texture and micro structure
• resolution better than 0.2 nm

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Surface area, pore size, pore volume determination

Determination of surface area and pore distribution of catalysts is important to understand


the extent of dispersion possible for the active metals. Higher surface area of support
results in higher dispersion of the active metals. Hence supports of higher surface area are
desirable.

Pores are usually formed during drying or calcination of hydroxides precipitates or gel.
The size and number of pores determines the internal surface area. Pore size also
determines the accessibility of reactants to the active sites and the ability of diffusion of
products back to the bulk fluid. Hence pore structure and surface area must be optimized
to provide maximum utilization of active sites for a given feed stock.

Working principle and instrumentation

The basic components of volumetric physical adsorption analyzer as shown in Fig. 1 are:

1) Analysis manifold of accurately known volume and temperature

2) Vacuum system with valve to manifold

3) Source of adsorptive gas (typically, N2) with valve to manifold

4) Pressure transducer and temperature sensor

5) Sample tube connected to analysis manifold

6) Liquid nitrogen bath

Determination of internal surface area is based on adsorption and condensation of N2 at


liquid N2 temperature, 77K. Initially, the sample is evacuated at 293-523 K (120-250 oC)
followed by cooling to 77 K by liquid N2. Then gradually the partial pressure of nitrogen
above the sample is increased. Some quantity of gas will be adsorbed by the sample and
removed from the gas phase. After stabilization the equilibrated pressure is recorded and
amount of nitrogen adsorbed at each equilibrated pressure is noted. The isotherm, volume
adsorbed as function of relative pressure p/po, is plotted from the data. The pressure over
the sample is gradually increased until pressure reaches near saturation pressure, by when

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the complete adsorption isotherm is developed. The desorption isotherm is measured by


a step-wise reduction in pressure until a low pressure over the sample is achieved.
Although the volumes are adsorbed at different conditions, the values are reported at STP
conditions. Fig. 2 shows a typical N2 adsorption and desorption isotherm at 77 K for
alumina.

Adsorptive gas
(N2)
Valve
Analysis manifold

To vacuum pump Temperature sensor


Pressure Transducer
for evacuation

Sample tube

Liquid nitrogen
container

Fig. 1. Basic components of volumetric physical adsorption analyzer

Isotherm
350

300

250
Volume Adsorbed cc/g (STP)

200

150

100

50

0
0 0.2 0.4 0.6 0.8 1

Relative Pressure Ps/Po

Fig. 2. A typical N2 adsorption and desorption isotherm at 77 K for alumina

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Adsorption using Argon and Krypton

Krypton is used as adsorbate at 77 K for low surface area analysis while, Argon
adsorption at 77 K and liquid argon temperature (87K) is often used for micro and
mesopores analysis.

To measure very low surface area the number of molecules trapped in the void volume of
sample cell needs to be reduced. The number of molecules left in void volume can be
reduced by using adsorbate such as Krypton with low vapor pressure at liquid nitrogen
temperature. The saturation pressure of Krypton at liquid nitrogen temperature is 0.35
kPa which is much lower compared to that of N2 (101.3 kPa). Consequently the number
of Krypton molecules in free space of sample cell, at any given relative pressure, is
significantly reduced compared to that of nitrogen at liquid nitrogen temperature, though
amount of adsorption will be only slightly less. Hence, Krypton adsorption at 77 K is
much more sensitive and can be applied to measure surface areas down to 0.05 m2. The
cross sectional area used for Krypton is 0.202 nm2.

For analysis of ultramicropores less 0.7 nm, the nitrogen adsorption at 77 K is not
satisfactory. The pore width of 0.7 nm corresponds to bilayer thickness of nitrogen
molecule. For ultramicropores, pore filling occurs at relative pressure of 10-7 to 10-5,
where the rate of diffusion and attainment of adsorption equilibration is very slow.
Consequently measurement becomes time consuming and may also cause non-
equilibrated adsorption isotherms with erroneous results. On the other hand argon fills the
micropores of dimension 0.4-0.8 nm in most cases at much higher relative pressure as
compared to nitrogen. This leads to accelerated diffusion and equilibration process and
result in reduction of analysis time as well as increase in accuracy. Argon adsorption is
advantageous for pore size analysis of zeolites and other microporous materials.

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The typical surface area values of different supports and catalysts are summarized in
Table 1.

Table 1. Typical surface area values of different support and catalyst.

Support/catalyst BET surface Application


area

m2/g

Activated carbon 500-2000 Used as support for various process

Zeolites 500-1200 Used as catalyst and support

Al2O3-SiO2-Zeolites 100-600 Fluid catalytic cracking catalysts

Ni/Al2O3 100-150 Methanation catalyst

Cu/Zn/Al2O3 Methanol synthesis catalyst

MnOx/Al2O3 140-180 Catalyst for total oxidation of volatile


organic carbon

Fe/K/Al2O3 20 Ammonia synthesis catalyst

Determination of surface area using BET Equation

As discussed earlier (lecture 4), the BET equation describes the relationship between
volume adsorbed at a given partial pressure and the volume adsorbed at monolayer
coverage. BET equation can be written in the form :

p 1 c −1 p
= + --------------- (1)
v ( p0 − p ) vm c vm c p0

p = partial pressure ; po =saturation pressure at the experimental temperature ;


v = volume adsorbed at p; vm = volume adsorbed at monolayer coverage ; c =
constant

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p
Monolayer coverage is determined using BET equation. The is plotted as a
v ( p0 − p )

p p
function of . The plot is linear in the range of relative pressures = 0.05 - 0.3. At
p0 p0

higher relative pressure p/po, the BET plot deviates from linearity as non-ideality or pore
condensation was not accounted for the derivation of BET equation.

Slope and intercept of this linear plot is used for determination of monolayer capacity vm .

The intercept and slope from the plot is given as

1 ( c − 1)
Intercept  = Slope =
cvm cvm

1
Then the monolayer volume vm is given as , vm = ( STP )
slope + intercept

The total number of N2 molecules adsorbed corresponding to monolayer volume vm can


be calculated as

vm (m3 ) × 6.02 ×1023 (molecules / mol )


No. of N 2 molecules =
0.0224 (m3 / mol )
Now , each adsorbed N2 molecule occupies an area of surface comparable to its cross
section area of 0.162 nm2.

 vm (m3 ) × 6.02 ×1023 (molecules / mol ) 


SA ( m 2
)  3  ×16.2 ×10
−20
(m 2 / N 2 molecule)
 (0.0224 m / mol ) 

Or SA ( m 2 ) = vm ( m3 ) × 4.36 ×106 (m −1 ) = 4.36 × 106 vm

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Solved problem :

1.Nitrogen was employed to determine the surface area of 1.0 g sample of silica gel and
results obtained shown in table below. The sample of silica gel was maintained at the
normal boiling point of liquid nitrogen (77K). One molecule of nitrogen occupies 16.2 ×
10-20 m2 area of plane surface. Calculate the specific surface area of silica gel by the BET
method. The saturated vapor pressure p0 of nitrogen at 77K is 101.3 kPa.

Equilibrium Pressure, p [kPa] 5.0 6.3 7.5 9.0 11.2

Volume adsorbed, (STP), V × 106 6.7 7.0 7.2 7.4 7.7


[m3]

Solution :

p 1 C −1 p
The BET equation in following form is used. = +
V ( p0 − p ) Vm C Vm C p0

p p
The is plotted as function of . The plot is shown in Fig. 3.
V ( p0 − p ) p0

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Table 1. Calculation for plot of BET equation

v p po p/po p/[v(po-
p)]
m3 kPa kPa
m-3

6.7E-06 5 101.3 0.049 7.75E+03

7.0E-06 6.3 101.3 0.062 9.47E+03

7.2E-06 7.5 101.3 0.074 1.11E+04

7.4E-06 9 101.3 0.089 1.32E+04

7.7E-06 11.2 101.3 0.111 1.61E+04

Fig. 3. Linear plot of BET equation

Intercept = 943.5 m- 3 ; Slope = 137486 m- 3

1 1
Monolayer volume =
Vm = = 7.22 ×10−6 m3 (STP)
slope + intercept 137486 + 943.5

Then surface area for 1 gm sample can be determined as :

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 7.22 ×10−6 m3 × 6.02 ×1023 molecules / mol 


SA  −6 3  ×16.2 ×10−20 m 2 / N 2 molecule
 22400 ×10 m / mol 

= 31.4 m2

As initially 1 gm sample was used, specific surface area of sample = 31.4 m2/g

Book reference

• S. Lowell, Joan E. Shields, Martin A. Thomas ,Characterization Of Porous Solids


And Powders: Surface Area, Pore Size And Density - Springer, 2006
• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications,
2001
• J. M. Thomas & W. J. Thomas, Principles and Practice of Heterogeneous Catalysi,
VCH, 1997
• Sam Zhang, Lin Li, Ashok Kumar, Materials Characterization Techniques, CRC
Press, 2009
• Y. Leng, Materials Characterization: Introduction to microscopic and spectroscopic
methods, John Wiley & Sons, 2008

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Lecture 11

Pore analysis

In general, catalyst consists of pore in the range of, micropore, mesopore or macropore
depending on the preparation conditions and compositions. To determine the pore size
distribution within the catalyst, pore analysis is essential. Knowing the pore size
distribution gives an idea about accessibility of the reactants to the active sites. The pore
analysis consist of determining the average pore size, average pore volume and pore size
or pore volume distribution.

Total pore volume and average pore size

Total pore volume is defined as the liquid nitrogen volume at a certain p/po (=0.95).Total
gas adsorbed at certain p/po (=0.95) is converted to liquid volume assuming pores are
filled with liquid adsorbate
Vgas ( STP )
V p =Vliq = × 34.6 =Vgas × 1.54 × 10−3 cm 3
22.4 × 10 3

where , 34.6 cm 3 / mol = molar volume of liquid nitrogen

Average pore size can be estimated from the pore volume. Assuming cylindrical pore
2V p
geometry average pore radius (r) can be expressed as: r =
S

Pore size

(a) By gas adsorption


Pore size and pore size distribution can be determined using Kelvin equation. Kelvin
equation relates equilibrium vapor pressure (p) of a liquid contained in a capillary to
equilibrium pressure of the same liquid over a free surface (po) :

γ = surface tension of liquid nitrogen


θ = contact angle ( usually zero for liquid N 2 )
p −2γ Vliq cos θ Vliq = the molar volume of liquid nitrogen
ln = -------------------- (1)
po rRT r    = radius of pore
R   = gas constant
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At any equilibrium pressure, p, the pore of radius less than ‘r’ will be filled with the
condensed vapor. Application of Kelvin equation to all points of an isotherm at relative
pressure greater than that corresponding to monolayer volume where capillary
condensation begins to occur, will yield information concerning the volume of gas
adsorbed in pores of different radii. For nitrogen as adsorbate and substituting values of
various constants, the Kelvin equation can be written as

P −2γ Vliq cos θ


ln =
Po rRT

p
Or rk ( nm ) = 0.41 log (2)
p0

γ = 8.72 mN/m
θ =0
Vliq 34.68 ×10−6 m3 / mol
=
T = 77 K
R=8.314 J / K mol

The ‘rk’ is the radius into which condensation occurs at the required relative pressure.
This radius is called Kelvin radius. However, Kelvin radius is not the actual pore radius
since some adsorption has already occurred on the pore wall prior to condensation
leaving a central core of radius rk . Conversely, an adsorbed film remains on the wall
when evaporation of the centre core takes place.

Condensed
liquid t
Adsorbed
2rk film

2r

Fig. 3. Schematic showing Kelvin radius and actual pore radius during pore condensation

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Then if ‘r’ is the actual pore radius and the thickness of the adsorbed film is t (Fig. 3)
then

2γ Vliq p
r (nm) = rk + t = + t = 0.41 log + t (3)
p p0
RT ln
po

Pore size distribution can be obtained by the analysis of either adsorption or desorption
isotherm branches. Kelvin equation as described is applied to the desorption branch of
hysteresis loop as it is more appropriate to assign wetting angle to a pore filled with
liquid that possess a well defined meniscus. If ‘h’ is the effective height of a monolayer,
V 
then the thickness of adsorbed layer ‘t’ is given as t =   h . Here ‘V’ is the volume of
 Vm 
gas adsorbed and ‘Vm’is the volume of adsorbed monolayer. When the packing of
adsorbate is hexagonal, then for nitrogen h = 3.6 A0 and for cubic packing h= 4.3 A0 =
0.43 nm. The ‘t’ at a given relative pressure can also be calculated using Halsey equation
1 1
 3  3
 5  o  5 
t=
3.54 ×   ( A) =
0.354 ×   nm (4)
 2.303 × log p0   2.303 × log p0 
 p   p 

Pore size distribution

Most common method for determination of pore size distribution is BJH (Barrett-Joyner-
Halenda) method. Assumptions are:

(i) Condensation occurs in pores when a critical relative pressure is reached


corresponding to the Kelvin radius ‘rk’
(ii) When evaporation or condensation occurs, a multilayer of adsorbed film exist on the
pore wall and this film has same depth/thickness as the adsorbed film on a non porous
surface

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(iii) Actual pore volume evaporation is composed of the volume evaporated out of the
central core plus the volume desorbed from the film left on the pore walls

Steps for determination of pore size distribution are as follows:

1. p/p0 and Vgas (STP, cm3/g) data obtained directly from isotherm.
2. Then Kelvin radius ‘rk’is calculated from Kelvin equation using zero wetting
angle for N2 from equation(2).
3. Then, the film thickness t calculated from Halsey equation (4) at each p/p0.
4. Then the pore radius r calculated from equation (3).
5. Mean values of rk and r in each decrement are calculated from successive entries.
6. Change in film thickness Δt is calculated from difference of successive values of t .
7. Then ΔVgas , that is the change in adsorbed volume between successive p/po values,
is determined by subtracting successive values .
8. Thereafter, ΔVliq that is the volume of liquid corresponding to ΔVgas is calculated as
follows

∆Vgas
∆Vliq = ∆Vgas × 1.54 × 10−3 cm 3 / g
× 34.6 =
22.4 × 10 3

9. Then ΔtΣS is determined. This represents the volume change of the adsorbed film
remaining on the walls of the pores from which the central core has previously
evaporated . This volume is the product of the film area ∑S and the decrease in film
depth Δt
10. Actual pore volume evaporated, Vp. is then determined. Actual pore volume
evaporated is composed of the volume evaporated out of the centre core plus the
volume desorbed from the film left on the pore walls, For a pore of length L,
Vliq π rk2 L + ∆t ΣS
∆=
2
−
V p  −   ∆Vliq − ( ∆t ΣS × 10−4 )  cm 3 / g
r
Now , V p = π r 2 L . By combining
=
 
 rk 

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11. The surface area of the pores walls can be calculated from pore volume by :
2V p
=
S −
× 104 m 2 , Vp in cm3/g and r in A0
r

An elaborate example of pore size distribution work table can be seen in Lowell et al. for
more understanding.

(a) (b)

0.04
Pore Volume (cc/g*nm)

0.03

0.02

0.01

0
0 5 10 15 20 25 30 35 40
Pore Diameter (nm)

Fig. 4. Pore volume distribution of titania samples calcined at 400 0C

(a) differential (b) cumulative

Pore size distribution can be represented both in differential and cumulative ways. The
Fig. 4(a) shows the differential BJH pore distribution of titania sample calcined at 400 0C.
The figure shows that for the given sample pores were in the range of 2-10 nm. The
corresponding cumulative pore distribution is shown in Fig. 4(b).

(b) By mercury intrusion

For macropores materials with pore diameter greater than 50 nm, the mercury intrusion
method is preferred. Due to non-wetting nature of mercury on oxide supports, intrusion is
met with resistance and mercury is forced to enter the pores of material under pressure.
The pore radius ‘r’ is related to the applied pressure P as

( −2γ cos θ )
P = -----------------(5)
r

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The wetting or contact θ angle between mercury and solid is on average lies in the range
130-1400 and surface tension of mercury is 0.48 N/m2. p is in atm and r in nanometers.

As can be observed from equation (5) smaller the pore radius higher is the pressure
needed for mercury to intrude in the pore. At low pressure of 0-2 atm, mercury
penetrates voids between particles. At moderate pressure range of 3-500 atm large
macro pores are filled. At further higher pressure range of 500-2000 atm, smaller macro
pores and large mesopores are progressively filled. This technique is satisfactory for
pores down to 3-5 nm dia . Maximum diameter that can be measured is usually 105 nm.
Mercury intrusion method is carried out in the instrument known as mercury porosimeter.
In a typical mercury porosimeter data, volume of mercury penetrating into pores is
plotted as a function of applied pressures.

Mercury r2 r3
r1

Sample
Pressure 1 Pressure 2 Pressure 3

Pressure 1< Pressure 2 < Pressure 3 as r1 > r2 > r3

Fig. 5. Intrusion of mercury into pores of various sizes. Here ‘r’ represents the radius of pores.

The pressure required for filling up the pores as a function of pore size is schematically
shown in Fig.5. As pore radius decreases in the order r1 > r2 > r3, requried pressure for
filling the pores increases in order of Pressure 1< Pressure 2 < Pressure 3.The available
instruments can measure pore size up to 2 nm using a maximum operating pressure of
about 400 MPa.

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Table 1. Typical pore volume values of different support and catalyst.

Support/catalyst Pore Application


volume

cm3/g

Activated carbon 0.6-0.8 Used as support for various process

Zeolites 0.5-0.8 Used as catalyst and support

Al2O3-SiO2-Zeolites 0.1-0.9 Fluid catalytic cracking catalysts

Book reference

• S. Lowell, Joan E. Shields, Martin A. Thomas ,Characterization Of Porous Solids


And Powders: Surface Area, Pore Size And Density - Springer, 2006
• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications,
2001
• J. M. Thomas & W. J. Thomas, Principles and Practice of Heterogeneous Catalysis,
VCH, 1997
• Sam Zhang, Lin Li, Ashok Kumar, Materials Characterization Techniques, CRC
Press, 2009

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Lecture 12

X-Ray Diffraction

X-ray diffraction (XRD) is an effective method for determining the crystal structure of
materials. It detects crystalline materials having crystal domains greater than 3-5 nm. It is
used to characterize bulk crystal structure and chemical phase composition.

Crystalline & Amorphous materials

Materials can be classified as

o Crystalline material : Crystalline material can be single crystal or


polycrystalline
o Amorphous material

Crystalline material

Crystalline materials are composed of atoms arranged in a regular ordered pattern in three
dimensions. This periodic arrangement is known as crystal structure. It extends over
distance much larger than the interatomic separations. In a single crystal, this order
extends through the entire volume of the material. There are seven crystal systems: cubic,
tetragonal, orthorhombic, rhombohedral, hexagonal, monoclinic and triclinic. Different
crystal structures are based on framework of one of the 14 Bravais lattice.

Parallel planes of atoms intersecting the unit cell are used to define directions and
distances in the crystal. The ‘d spacing’ is defined as the distance between adjacent
planes .The orientation and interplaner spacing (d) of these lattice planes are defined by
three integers h,k,l called Miller Indices. The (hkl) designate a crystal face or family of
planes throughout a crystal lattice.

Polycrystalline materials consist of many small single crystal regions called grains.
Grains are separated by grain boundaries. The grains can have different shapes and sizes
and are disoriented with respect to each other.

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Amorphous materials: When the atoms are not arranged in a regular periodic manner,
the material is called amorphous. Such materials posses only short range order ( distance
less than a nanometer).

X-Ray Diffraction :

X-ray is a form of electromagnetic radiation having range of wavelength from 0.01-0.7


nm which is comparable with the spacings between lattice planes in the crystal. Spacing
between atoms in metals ranges from 0.2-0.3 nm. When an incident beam of X-rays
interacts with the target atom, X-ray photons are scattered in different directions.
Scattering is elastic when there is no change in energy between the incident photon and
the scattered photon. In inelastic scattering, the scattered photon loses energy. These
scattered waves may superimpose and when the waves are in phase then the interference
is constructive and, if out of phase, then destructive interference occurs. Atoms in crystal
planes form a periodic array of coherent scatterers. Diffraction from different planes of
atoms produces a diffraction pattern, which contains information about the atomic
arrangement within the crystal.

Bragg’s law

The X-ray beams incident on a crystalline solid will be diffracted by the crystallographic
planes. Bragg’s law is a simple model explaining the conditions required for diffraction.
It is given as n l = 2d hkl sin θ , where d hkl is the spacing between two planes hkl , n is an

integer and l is the wavelength. For parallel planes of atoms, with a spacing dhkl between
the planes, constructive interference occurs only when Bragg’s law is satisfied. In
diffractometers, the X-ray wavelength is fixed. Consequently, a family of planes
produces a diffraction peak only at a specific angle θ. The spacing between diffracting
planes of the atoms determines the peak positions. The peak intensity is determined by
the atoms in the diffracting plane. Fig. 1 explains the Bragg’s law. Two in-phase incident
waves, beam 1 and beam 2, are deflected by two crystal planes (Z and Z1). The diffracted
waves will be in phase when the Bragg’s Law, nλ = 2d sin θ, is satisfied. In order to keep
these beams in phase, their path difference (SQ + QT ) has to equal one or multiple X-ray
wavelengths (nλ) i.e SQ + QT = nλ or SQ + QT = 2PQ sin θ = 2d sin θ = nλ. Hence the

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path difference depends on the incident angle (θ) and spacing between the parallel crystal
planes (d ).

Incident beam Diffracted beam



λ1
2 2΄

P θ
θ
Z Z΄
θ θ dhkl
S T
Z1 Z1΄
Q

Fig. 1. Braggs analysis for X-ray diffraction by crystal planes

Working principle and Instrumentation

The instrument is called an X-ray diffractometer. In the diffractometer, an X-ray beam of


a single wavelength is used to examine the specimens. By continuously changing the
incident angle of the X-ray beam, a spectrum of diffraction intensity versus the angle
between incident and diffraction beam is recorded.

The main components of diffractometer are

• X-ray Tube: the source of X Rays.


• Incident-beam optics: to condition the X-ray beam before it hits the sample
• Goniometer: the platform that holds and moves the sample, optics, detector, and/or
tube
• Sample holder
• Receiving-side optics: to condition the X-ray beam after it has encountered the sample
• Detector: to count the number of X Rays scattered by the sample

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The basic components of the diffractometer are shown in Fig 2. The ‘θ’ is the angle
between the X-ray source and the sample, whereas 2θ is the angle between the incident
beam and the detector. The incident angle θ is always half of the detector angle 2θ. The
basic function of a diffractometer is to detect X-ray diffraction from materials and to
record the diffraction intensity as a function of the diffraction angle (2θ). The X-ray
radiation generated by an X-ray tube passes through Soller slits which collimate the X-
ray beam. The X-ray beam passing through the slits strikes the specimen. X-rays are
diffracted by the specimen and form a convergent beam at the receiving slits before they
enter a detector.

Detector
X-ray tube

θ

sample

Fig. 2. Basic components of X-ray diffractometers

The diffracted X-ray beam passes through a monochromatic filter to suppress


wavelengths other than Kα radiation and decrease any background radiation, before being
received by the detector. The Kα radiation is generated by bombarding of target surface
(Cu, Fe, Cr) by accelerated electrons. Most commonly a copper target is used generating
Kα wave length of 0.154 nm.

Relative movements among the X-ray tube, specimen and the detector ensure the
recording of diffraction intensity in a range of 2θ.

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An instrument can be operated in two ways:

• tube is fixed, the sample and the detector rotates (THETA : 2-THETA
arrangement)
• sample is fixed and the tube and the detector rotates (THETA:THETA
arrangement)
Powder diffraction

A single crystal produces only one family of peaks in the diffraction pattern. A
polycrystalline sample contains thousands of crystallites. Therefore, all possible
diffraction peaks are observed. Powder diffraction is used for characterization of
polycrystalline materials. The basic assumption of powder diffraction is that for every set
of planes, there are statistically relevant number of crystallites that are properly oriented
to diffract the incident beam. The diffraction pattern is the fingerprint of any crystalline
phase. The position, intensity, shape and width of the diffraction lines gives information
on the samples. Powder diffraction data consists of a record of photon intensity versus
detector angle 2Ө. Diffraction data can be reduced to a list of peak positions and
intensities. Each dhkl corresponds to a family of atomic planes (hkl). However, individual
planes cannot be resolved in by this method; this is a limitation of powder diffraction
versus single crystal diffraction

Applications

Catalysts are extensively characterized by XRD technique.The major applications of


XRD are discussed below.

1. Phase Identification
The catalysts are generally composed of mixture of several phases. The diffraction
pattern for each phase is as unique as a fingerprint. Phases with the same chemical
composition can have drastically different diffraction patterns. Phase identification is
based on the comparison of the diffraction pattern of the specimen with that of pure
reference phases or with a database. Databases such as the Powder Diffraction File (PDF)
contain lists for thousands of crystalline phases. The PDF contains over 200,000
diffraction patterns. Modern computer programs can determine the phases present in a

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sample by quickly comparing the diffraction data to all of the patterns in the database.
Various crystalline phases can be quantified based on the fact that each phase of the
mixture gives its characteristic diffractogram independently of the others and the
intensity depends on the amount present in the mixture. The intensity of the diffraction
line (hkl) from a phase α is given by

X α = weight fraction of phase α


ρα = mass fraction of phase α
Kα ( hkl ) × X α ( m / ρ )m = mass absorption coefficient of the mixture
Iα ( hkl ) =
ρα × ( m / ρ )m
Kα ( hkl ) = constant for a given phase structure α ,
diffraction line (hkl)and set of exprimental conditions
Peak intensities are generally measured from peak heights on the assumption that peak
height is proportional to peak area

2. Determination of average crystallite size


Ideally, a Bragg diffraction peak is a line without width. In reality, diffraction from a
crystal specimen produces a peak with a certain width. This is known as peak broadening.
The peak width depends on the size of the crystals. Peak width is inversely related to
crystal size; that is, peak width increases with decreasing crystal particle size.

The average crystallite size can be determined by Scherrer formula using elementary line
broadening analysis. The Scherrer formula assumes that the breadth of the diffraction
peak of crystallites (small single crystals) mainly depends on the characteristics of
crystallites (size and the defect in the lattice). Elementary analysis of the broadening
assumes that lattice deformation is negligible. According to Scherrer, the thickness of
crystallite, L, can be determined by

kl = =
k constant ; l wavelength of X-ray source ;
L=
β cos θ β = breadth of diffraction profile = Full width at half maxima
θ = half of the diffraction angle/Bragg angle

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The diffraction corresponding to the most intense peak is selected to calculate the average
crystallite size using Scherrer relation. The Scherrer formula assumes that crystallite size
is the major source leading to line broadening effect of the diffractions peaks, but there is
always a line broadening can also be due to instrumental factors such as slit width,
sample size, imperfect focusing or misalignment of diffractometers.

3. Spacing between atomic planes of a crystal


Based on Bragg’s Law, information on spacing between atomic planes can be obtained
when constructive interference occurs. Knowing the spacing of crystallographic planes
by diffraction methods, the crystal structure of materials can be determined. The plane
spacing of cubic crystal is related to the lattice parameter (a) by the following equation.
a
d hkl =
h2 + k 2 + l 2

From Braggs Law, nλ = 2d sin θ .

Combining ,

n 2l 2 2
2 (
=
sin θ
2
h + k2 + l2 )
4a

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Examples

1. XRD pattern of oxide supports


Titania and zirconia are used as catalyst support or as active catalyst itself. They can be
identified from their XRD pattern by comparison with the standard files. For any
unknown sample the peaks are identified by comparison with the standard data. For
oxides calcined at 400-500 0C, the typical XRD profiles of titania and tetragonal zirconia
are shown in Fig 3.

TiO2
Intensity (a.u.)

ZrO2

20 30 40 50 60 70 80

Fig. 3. XRD profiles for titania and zirconia prepared by precipitation method

Solved problem

1. A cubic crystal was placed in an x-ray diffractometer using incoming x-rays with a
wavelength λ = 0.154 nm. The various peak intensities recorded at different 2θ values
are given in following table.

2θ ( deg) 40.3 58.3 73.2 154.2 131.2

hkl 110 200 211 400 321

Relative intensity 100 15 23 2 18

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Determine the followings


i. Calculate the crystal size ( Given, k=0.9; β = 0.0098)
ii. Calculate the value for the lattice constant (Assume first order diffraction with n =
1.)
Solution

i. The crystal size can be calculated using the peak corresponding to 2θ = 40.3 having
highest peak intensity.
Hence, k = 0.9 ; β = 0.0098; λ=0.154 nm; θ=20.15, the crystal size L can determined
using the Scherrer equation as follows

kλ 0.9 × 0.154 0.1386


=L = = = 15.1 nm
β cos θ β × cos ( 20.15 ) 0.0098 × 0.9387

ii. The plane spacing of cubic crystal is related to the lattice parameter (a) by the
following equation.

a2
d 2
= 2 [1]
h + k2 + l2
hkl

From Braggs Law,


nλ = 2d sin θ
[2]
or, n2 λ2 = 4d2 sin2 θ

n 2λ 2
or, d =
2
[3]
4sin 2 θ

From [1] and [3] Combining ,

n 2l 2
=a2
4sin θ
2 ( h2 + k 2 + l 2 )

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Using the peak corresponding to 2θ = 40.3 having highest peak intensity with [hkl] value
of [110] the lattice constant ‘a’ for cubic crystal can be calculated as follows.

Or

12 × 0.1542
2 (
=a2 = 12 + 12 + 0 ) 0.1 nm =
[ sin 20.15 0.3436]
4 ( sin 20.15 )

Or, a = 0.342 nm

Book reference

• Sam Zhang, Lin Li, Ashok Kumar, Materials Characterization Techniques, CRC
Press, 2009
• Y. Leng, Materials Characterization: Introduction to microscopic and spectroscopic
methods, John Wiley & Sons, 2008
• Edited by R.E. Dinnerbier and S. L. J. Billinge, Powder Diffraction :Theory and
Practice , RSC Publishing, 2008
• J. M. Thomas & W. J. Thomas, Principles and Practice of Heterogeneous Catalysi,
VCH, 1997

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Lecture 13

Chemisorption

In many catalysts, active metals are deposited on the surface of the support such as in
Pt/Al2O3, Pt/C, Ni/Al2O3 etc. These metals act as active sites in various oxidation states

including in zero valence state. The location and state of the active metal on the support
largely depends on the preparation method of the catalyst. When prepared by
impregnation method, more active metals are expected to concentrate on the surface of
support, whereas in bulk preparation method active metals are trapped more within the
bulk matrix. Further, these metals usually exist as clusters on the support surface and
thereby, only a fraction of the total deposited metal is actually exposed to the incoming
reactant molecules for participation in a reaction.

N 
The dispersion (D) of metal is defined as D= S 
 NT 
where ,

Ns = total no. of exposed surface atoms

N = total no. of metal atoms present in the sample


T

Metal cluster

Support

Fig. 1. Metal cluster on support surface

Chemisorption technique gives direct measurement of the number of exposed surface


atoms. This method measures quantity of gas adsorbed selectively on the metal at
monolayer coverage.

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This technique is mainly used to study :


(1) metal dispersion and
(2) active metal area.
In this method, the sample is exposed to a gas that can chemisorb on the active metal. At
monolayer coverage, the average number of surface metal atoms associated with
adsorption of each gas molecule is determined. Accurate determination of metal
dispersion and the active metal area is possible if stoichiometry of the chemisorption
reaction is known. Pulse method is frequently used to determine the number of gas
molecules adsorbed on the catalyst surface.

For a given catalyst, the adsorbate gas is chosen to minimize adsorption on the support
and to have an irreversible (or weakly reversible) chemisorptions on the metal. H2 and

CO are the most commonly used adsorbate gases.

Hydrogen Chemisorption
H adsorbs dissociatively on metals according to the equation :
2

H 2 + 2M s → 2 M s − H

Ms represents a surface metal atom.

The chemisorption stoichiometry n is defined as the number of metal atoms to which one
adsorbate gas molecule can attach. In case of hydrogen chemisorption, one hydrogen
molecule attaches with two metal atoms; hence n = 2 .

CO chemisorption

The CO adsorption is considerably more complex. The CO can chemisorb in various


forms on metals such as Fe, Ni, Ru, Pt , Pd. The chemisorption stoichiometry varies with
temperature, metal dispersion, metal loading and preparation. CO can be chemisorbed :
1. Dissociatively (CO: n = 2 ) or
2. Associatively
 Linear (n =1)
 Bridged ( n = 2)

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 Multi-bonded species (n = 3)
The relative proportion of the various forms depends on temperature, pressure and metal
particle size.

Adsorbate gas choice

For a given catalyst, the adsorbate gas should be chosen such that it interacts irreversibly
with metal or have very weak reversible interaction. The adsorbate should have minimum
adsorption on the support. Most commonly used adsorbate for metal characterization is
hydrogen and CO. Other gases such as O2, N2O, NO, N2 etc. are also used depending on
the specific application. The CO can chemisorb in different forms on metals such as iron,
nickel, ruthenium, palladium, rhodium and platinum. Not knowing the exact
stoichiometric relation can introduce error. The main difficulty is the formation of metal
carbonyl, which are volatile as in case of nickel and rhodium. However, CO
chemisorption is better suited when hydrogen can be absorbed into the metal (palladium
hydride formation) or significantly adsorbed on support (such as carbon support). Oxygen
chemisorption is also used. However, possibility of formation of metal oxides with
variable stoichiometry may cause errors. Main application of oxygen adsorption
measurement is hydrogen-oxygen titration. For cases, when interaction of metals with H2
or CO is very low and interaction with oxygen is excessively strong resulting in bulk
oxidation, such as for Cu or Ag, the adsorptive decomposition of nitrous oxide can be
used.

Working principle and instruments


In pulse chemisorption technique, initially the sample is reduced with hydrogen at
elevated temperature to convert the oxide to metallic form (such as NiO to Ni) .Then, the
sample is flushed with an inert gas at elevated temperature, such as helium, to remove
traces of any adsorbed gases. Then, sample is cooled to the analysis temperature, with
inert gas flowing. Successive small pulses of adsorbate gas (of known volume) are
injected in the flow of inert gas by a syringe or loop at the desired temperature. Pulses of
adsorbate gas are continued to be injected until the catalyst surface is saturated. The Fig
2 shows a typical plot of peak area of adsorbate gas as function of number of pulse
injected. As the figure shows, the first pulse corresponds to negligible peak area

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suggesting that most of the injected gas is adsorbed. For second pulse the peak area
increased compared to the first suggesting lesser amount of gas adsorbed compared to
first injection. As the number of pulse increases peak area gradually increases
corresponding to decreased amount of gas being adsorbed. Finally the peak area becomes
constant corresponding to the area of pulse volume. The constant areas are shown by
pulse number 6 and 7 in the Fig 2. The amount of gas adsorbed is obtained by
calculating the difference between the volume of each pulse and the fraction of H2 not

adsorbed. The total amount of gas chemisorbed can be obtained from the number of
consumed pulses. The schematic diagram of equipment for pulse chemisorption is given
in Fig. 3.

Peak Area of
adsorbate gas

1 2 3 4 5 6 7

Pulse number

Fig. 2. A typical plot of peak area vs pulse number of adsorbate gas

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Pretreatment gas Pulse

Thermocouple

Sample tube
TCD Purge

Furnace

Carrier Exit
gas

Fig. 3. Schematic diagram of equipment for pulse chemisorption

Calculations for determination of metal dispersion and active metal area :

1. The volume of active gas (CO or H2) injected,Vinj, can be calculated at STP
conditions using the equation below. Generally, the active gas is used as a gas
mixture, such as 10% CO in helium or 10 % H2 in argon.

Vsyr   = syringe volume injected , cm3


T P A
Vinj (STP) = Vsyr × std × amb × Tamb   =   ambient temperature, o C
Tamb Pstd 100
=Tstd    =
standard 
temperature 273K
Pamb = ambient pressure,  mmHg 
=Pstd   =
standard pressure   760mmHg
A  = %  active gas in gas-mixture

2. The volume of active gas chemisorbed is calculated using volume injected Vinj
and from area under the peaks as follows.
=
Vinj   volume  injected, cm3
Vinj  A n
Vads (STP, cm3 / gm) = × ∑ 1 − i  m = mass of the sample, gm
m i =1  A f 
A i =  area of peak i
 A f   = area of last peak

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3. Calculation of % Metal Dispersion

Vads
Moles of metal on surface of sample = n × moles/gm
Vg

M
Moles of total metal present in sample = moles/gm
m.w ×100

Moles of metal on surface of sample


D=
Moles of total metal present in sample

n =    stoichiometry factor
Vads m.w Vads   =   volume adsorbed, cm3 / gm 
D =×
n × ×100
Vg M =Vg   =
  molar volume gas at STP 22414 cm3 / mol
m.w.  =   molecular weight of the metal
M  =   %  metal loading

 V m.w 
Or %D = n × ads × ×100  ×100
 Vg M 
4. Active metal surface area per gram of sample

A m ( m 2 /gm ) = [ total number of surface metal atoms ] × [ cross section area of active metal ]

n   =    stoichiometry   factor
 V   Vads   =   volume adsorbed ,  cm3 / gm
A m ( m 2 /gm sample ) =  n × ads  × N A  × a
 Vg   =   molar volume of the gas at STP  = 22414 cm3 / mol 
 Vg  
N A   =   Avogadro’s number =  6.023 x 1 023 molecules / mol
=a    cross − sectional  area of  active  metal atom, m 2
Solved examples :
1. Calculate the metal dispersion and active metal area for
0.5 wt % Platinum on Alumina catalysts by CO pulse chemisorption. The areas of
the pulses are given in the table. Additional given data are :
Sample amount: 1gm ; Analysis gas: 10%CO/He; Carrier gas: He ; Temperature: 25 oC
; Pulse volume: 0.5cm3 ; stoichiometry factor of CO on Pt = 1.

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Peak No. 1 2 3 4 5 6 7

Peak area 0.0 0.0 0.0003 0.001 0.005 0.007 0.007

Solution :

i. Calculation of volume of Active Gas Injected From a Syringe 10 %CO /He

Tstd P A
Vinj (STP) = Vsyr × × amb ×
Tamb Pstd 100

Vsyr = syringe volume injected =0.5 cm3

Tstd = ambient temperature =22oC

Tamb = standard temperature 273K

Pamb = ambient pressure =743mmHg

Pstd = standard pressure=760mmHg

A = % active gas =10

273 743 10
Vinj (STP) = 0.5 × × × = 0.0448 cm3
( 25 + 273) 760 100
ii. Calculating Volume Chemisorbed:

Vinj n  A 
Vads = × ∑ 1 − i 
m i =1  Af 

Vinj = volume injected= 0.0448 cm3 ; m = mass of the sample = 1 gm

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Table 1. Calculation for volume of CO adsorbed on Pt supported on Alumina

(Vi ) ads Σ (Vi ) ads

 A 
 1 − i 
Peak Ai  Af 
Vinj A  n Vinj  A 
no. = × 1 − i =
m  A f 

i =1 m
×1− i 
 A f 

1 0 1.0000 0.0448 0.0448

2 0 1.0000 0.0448 0.0896

3 0.0003 0.9571 0.04288 0.1325

4 0.001 0.8571 0.0384 0.1709

5 0.005 0.2857 0.0128 0.1837

6 0.007 0.0000 0 0.1837

7 0.007 0.0000 0 0.1837

From Table 1, Af = area of last peak = 0.007

Volume of CO adsorbed on Pt supported on alumina = Vads = 0.1837 cm3/gm

iii. % Metal Dispersion:

n = stoichiometry factor, CO on Pt =1

Vads = volume adsorbed=0.l837 cm3/gm

Vg = molar volume of the gas at STP= 22414 cm3/mol

m.w. = molecular weight of the metal Pt = 195

M = % metal = 0.5

Moles of metal on surface of sample = n × Vads =



0.1837
=8.196 ×10−6 moles / gm
Vg 22414

Moles of total metal present in sample =


M 0.5
= = 2.564 ×10−5 moles / gm
m.w ×100 195 ×100

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8.196 ×10−6
=
%D = ×100 31.96 %
2.564 ×10−5

iv. Active Metal Surface Area (per gram of sample)

 V 
A m =  n × ads  × N A × a m 2 /gm sample
 Vg 

n = stoichiometry factor, CO on Pt=1

Vads= volume adsorbed= 0.1837 cm3/gm

Vg = molar volume of the gas at STP= 22414 cm3/mol

NA = Avogadro’s number = 6.023 x 1023 molecules/mol

a = cross-sectional area of active metal atom =0.08 nm2= 0.08 × 10-18 m2

 0.1837 
A m = 1×  × 6.023 ×1023 × 0.08 ×10−18 =0.395 m 2 /gm sample
 22414 

Book References

• G. Ertl, H. Knozinger and J. Weitkamp, Handbook of Heterogeneous Catalysis,


Vol. 2,WileyVCH, 1997.
• S. Lowell, Joan E. Shields, Martin A. Thomas ,Characterization Of Porous Solids
And Powders: Surface Area, Pore Size And Density - Springer, 2006

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Lecture 14

Thermo analytical techniques


For heterogeneous solid catalysis, understanding the interaction between fluids and active
sites on the solid surface is very important as it determine the surface reactivity. These
kinds of interactions are studied by many thermo analytical techniques, carried out
dynamically by application of linear temperature programme. These techniques involve
recording the surface or bulk interaction of solid catalysts with gaseous environment as
the temperature is increased, by continuously analyzing the gas phase composition. The
temperature programmed reduction (TPR) , temperature programmed oxidation ( TPO),
temperature programmed desorption (TPD), thermo gravimetric analysis (TGA) and
differential thermal analysis (DTA) are among the techniques used extensively for
characterization of catalysts.

Temperature programmed reduction (TPR)

Temperature programmed reduction is used to determine the reducibility of the


catalysts. In this method, reducible catalysts are exposed to flow of reducing gas
mixture typically H2 in Ar. The sample is initially pretreated in an oxidative atmosphere
(5% O2 in He) at predetermined temperature for 30 min and cooled to 250 0C in the
same mixture. The sample is then purged with helium and cooled to room temperature.
Then the preoxidized sample is reduced in a flow of H2 in argon from room
temperature to 900 0C. The carrier gas flow is maintained at a specified value (usually
30 ml /min). Temperature is linearly increased at the desired heating rate (usually 10
K/ min). The extent of reduction is continuously followed by measuring the
composition (H2 content) of the reducing gas mixture at the outlet of the reactor. The
total amount of H2 consumed is determined from the area under the peak and is used
to calculate the degree of reduction and average oxidation state of the solid material
after reduction.

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Fig.1. shows the arrangement used for TPR/TPO analysis. The same instrument as that
used for chemisorption can be used for this study.

Pretreatment gas

Sample tube
TCD Purge
Thermocouple

H2/Ar (TPR) Exit


Furnace
Or
Fig. 1. Schematic diagram for TPR/TPO analysis

Parameters that affects TPR profiles are :

• Heating rate, K/s


• Initial amount of reducible species, μmol
• Flow rate of reducing gas mixture, cm3 /sec
• Concentration of H2 in carrier gas, (μmol/cm3)
A higher heating rate increases the temperature of the sample faster compared to a slower
heating rate, consequently reduction peaks for the sample appear at comparatively higher
temperature than that at lower heating rate. On the other hand if the concentration of the
hydrogen in the reducing gas mixture is increased the samples are reduced more easily
resulting in sharper peaks at lower temperature compared to that at lower hydrogen
concentration. Change in gas flow rate has small effect. As the initial amount of reducible
species in samples increases, the area under the peak increases.

Hence the parameters have significant influence on shape of TPR profiles so that
comparison between experimental results obtain under different conditions is difficult to
make. Hence, for comparison, all TPR should be carried out at the same process
conditions.

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Application :

Solid catalysts containing reducible metals are characterized using TPR. Following
infomation can be gained from TPR curves :

1. Reduction peak temperature indicates the ease of reduction and degree of interaction
between different species present in the catalyst sample. A higher reduction
temperature indicates higher difficulty in reduction which can be attributed to the
greater degree of interaction between the active metal and support.
2. Multiple peaks indicate the presence of metal in different forms on the support having
different level of interaction between species and support.
3. The extent of reduction can be calculated as follows :

actual amount of hydrogen consumed


Extent of reduction =
theoretical amount of hydrogen consumed assuming complete reduction

The actual amount of hydrogen consumed is calculated from the area under the curve and
the theoretical amount is calculated from stoichiometry of reduction equation. The
average oxidation state of the solid material after reduction can be calculated thereafter.

4. Usually, reducibility of the catalysts can be correlated to its activity if the mechanism
involves redox reactions.
Examples

1. TPR of V2O5 catalysts


Amount of reducible species can be quantified by amount of H2 used by considering
reduction stoichiometry + 2H 2 → V2 O3 + 2H 2 O
V2 O5 as

The TPR profile of pure bulk vanadia is given in Fig. 2 . The presence of multiple peaks

is attributed to the multistep reduction sequence V2O5 → V6O13 → V2O4 → V2O3

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TCD Signal (a.u) )

200 300 400 500 600 700 800 900 1000

Temperature , 0 C

Fig. 2. Typical TPR profile of bulk vanadium oxide

2. TPR of supported nickel oxide catalysts

NiO is reduced in one step to metallic nickel according to the following equation :

NiO + H 2 → Ni + H 2 O

(A) TPR of NiO/C catalysts is shown in Fig. 3. NiO is reduced in one step. Presence of
single peak suggests NiO is present in one form.
TCD (a

0100200300400500600700800
Temperat r
Fig. 3. Typical TPR profile of nickel oxide supported on carbon

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(B) TPR of NiO supported on TiO2 catalysts is shown in Fig. 4. On titania, the multiple
reduction peaks are obtained for nickel oxide. The multiple peaks suggest the presence of
Ni species in various forms. The peak at the highest temperature corresponds to the Ni
species most difficult to reduce which can be attributed to the higher interaction with
support.

T.C.D. ( a.u. )

0 100 200 300 400 500 600 700 800 900


0
Temperature ( C )

Fig. 4. Typical TPR profile of nickel oxide supported on titania

Temperature programmed oxidation (TPO)


Temperature programmed oxidation is used for investigation of the redox behavior of
catalysts particularly when applied in cyclic TPR-TPO experiments. The equipment and
experimental procedure are the same as for the TPR study. The only difference is that the
sample should be in reduced form so that it is oxidized in the carrier gas containing
oxygen. The carrier gas generally used is O2/Ar mixture gas. Usually, it is carried out
after TPR and together gives a TPR-TPO cycle.

Temperature programmed desorption (TPD)


Temperature programmed desorption technique measures the desorbed molecules from
the sample surface. In TPD experiments, catalysts are pretreated in situ in oxidative
0
atmosphere at 100-200 C to remove any adsorbed species on the surface. Then, the
sample is equilibrated with an adsorbing gas or vapor saturated with the probe molecule
under well- defined conditions. After the excess gas is flushed out of the reactor, the
sample is heated in a flowing inert gas stream. The concentration of the desorbing gas in

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the effluent gas is continuously monitored by a thermal conductivity detector. The total
area under the curve gives the total amount of desorbed probe molecules. The same
instrument used for TPR can be used for TPD study. For TPD, a mass spectrometer
detector can also be used to detect the evolution of species from the surface back into gas
phase. TPD spectra are affected by inert gas flow rate, particle size, catalysts pore size
and catalysts bed depth.

Application
TPD studies gives :
• Type and amount of different forms of adsorbed species which correspond to the
presence of various peaks
• Relative bond strength between the adsorbate and surface which corresponds to
various peaks at different temperatures. Higher the desorption temperature
stronger the bonds and site strength.
TPD is extensively used for

• Study of acidic and basic sites on the surface


• Study of gas adsorbed on surface
• Study of organic compounds adsorbed on surface
For study of acidic and basic sites, mainly two types of probe adsorbate molecules are
used for TPD studies:

1. NH3 desorption for determining acidic sites


2. CO2 desorption for determining basic sites
Since NH3 is basic in nature it adsorbs on the acidic sites on the surface. The acidic sites
are quantified in terms of total ammonia molecules adsorbing on the surface in μmol/gm
of catalysts. However, ammonia adsorption cannot distinguish between Bronsted or
Lewis acid sites and only determines the total acidic sites. CO2 is an acidic gas and can
absorb on basic sites on the catalyst surface. This technique gives the total basic sites
quantified by total CO2 molecules adsorbed on the surface in μmol/g of catalyst.

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Adsorption study of any gases such as CO, H2, O2, CH4 on catalysts as required can
easily be done using TPD. Total area under the curve gives capacity of adsorptions and
multiple peak positions gives the bond strength.

Ammonia
desorbed
B
μmol/g

Temperature
Fig. 5. Typical TPD spectra observed

Fig. 5 shows a typical NH3-TPD spectrum observed for different samples. Curve A only
has one peak suggesting existence of one type of acidic sites on the sample to which
ammonia is attached, while curve B has two peaks and suggests two types of acidic
sites. The lower temperature peak suggests weaker bond strength and hence weaker
acidic sites, while the peak at the higher temperature means stronger bonds and hence
stronger acidic sites. The area under the curve gives the amount of weaker and
stronger sites. For curve B, concentration of the stronger sites is more. Similar kind of
conclusions can be drawn from CO2-TPD profiles corresponding to basic sites.

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Thermogravimetric Analysis (TGA)


In thermogravimetric analysis, the change in mass of samples is monitored with an
increase in temperature at specified gas environment and heating rate.

Thermocouple

sample

Carrier gas environment


Furnace

Balance

Fig. 6. Schematic diagram for thermogravimetric analysis technique

In this analysis, the sample is loaded in a small platinum crucible suspended from the arm
of a microbalance. The entire arrangement is placed within a small oven, temperature of
which is controlled and monitored. Analysis is carried out by raising the temperature of
the sample gradually in a flow of air or inert gas such as N2, Ar or He and the sample
weight (or percentage) is plotted against temperature. The parameters affecting the TGA
are : heating rate, amount of sample, carrier gas flow, nature of carrier gas etc.

Applications

TGA characterization is used to determine the thermal stability, content of moisture and
volatile material, if any, or decomposition of inorganic and organic material in the
catalysts. This method can also be used to study reaction kinetics with reactive gases
(e.g., oxidation, hydrogenation, chlorination, adsorption/desorption) as well as pyrolysis
kinetics (e.g., carbonization, sintering).

Only thermal processes that are associated with change in mass can be detected by TGA
process which makes its use rather limited. However for desorption, decomposition or
oxidation reaction, TGA can be used to gain useful information. The thermal stability of

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materials in both inert and oxidizing atmosphere can be determined by this technique. For
catalysts, information regarding moisture content , decomposition or any reactions
involving mass change that may happen during calcination / reactions conditions can be
determined using a similar gaseous environment. Any catalytic reaction that is
accompanied by mass change such as combustion or pyrolysis can be studied using TGA.
TGA can be also used to determine the extent of deactivation by deposition of coke. TGA
of deactivated sample in oxidizing atmosphere will remove the deposited coke of the
used catalyst and thereby the amount of deposited coke can be quantified.

Mass of

sample B

Temperature

Fig.7. Different TGA curves (A) single step change (B) multistep change (C) increasing mass

Fig. 7 shows some typical curves observed during TGA analysis. Curve A represents
change in a single step. This can be moisture removal or decomposition or reaction of the
material. For example, TGA of carbon in air is an example of this type of curve, where
carbon after reaching the specific temperature in air burn down oxidizes, producing CO2
and CO gases.

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The curve B corresponds to any change in multiple steps. The curve C on the other hand,
shows an increase in the mass of the sample. This is observed for oxidation of metals
such as oxidation of silver in air which results in gain in weight by formation of AgO2.
TGA does not give any information on processes which are not associated with mass
change such as phase change, melting or crystallization etc.

Examples
1. TGA of alumininium hydroxide

The Fig. 8A shows a typical TGA profile for aluminium hydroxide prepared by
precipitation method in nitrogen flow at heating rate of 10 K/min . The weight loss
corresponds to conversion of aluminium hydroxide to aluminium oxide by removal of
water.

2. TGA of activated carbon

The Fig. 8B shows a typical TGA profile for activated carbon in nitrogen flow at a
heating rate of 10 K/min. The initial weight loss at 100 0C is due to removal of moisture.
Since the carrier gas is inert, there is no further significant change in the weight of the
sample.

100
100

90 80
Weight loss %

80
Wt. loss (%)

60
70
40
60

50 A 20 B
40
0 100 200 300 400 500 600 700 800 0
0 200 400 600

0
Temperature (°C) Temperature C

Fig. 8. Typical TGA profile for (A) aluminum hydroxide (B) activated carbon

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Differential Thermal Analysis (DTA)

DTA consists of heating a sample and reference material at the same rate and
monitoring the temperature difference between the sample and reference. In this
method, the sample is heated along with a reference standard under identical thermal
conditions in the same oven. The temperature difference between the sample and
reference substance is monitored during the period of heating. As the samples undergo
any changes in state, the latent heat of transition will be absorbed/evolved and the
temperature of the sample will differ from that of the reference material. This
difference in temperature is recorded. Hence, any change in state can be detected
along with the temperature at which it occurs.
Thermocouple

sample reference

Furnace

Fig. 9. Schematic diagram for differential thermal analysis technique.

When an endothermic process occurs (ΔH positive) in the sample, the temperature of
sample (Ts) lags behind the temperature of reference (Tr). The temperature difference
ΔT= (Ts-Tr) is recorded against reference temperature Tr and the corresponding plot is
shown in Fig 10. In DTA, by convention, endothermic response is represented as
negative that is by downward peaks. When an exothermic process (ΔH negative) occurs
in the sample, the response will be in the reverse direction and the peaks are upward.
Since the definition of ΔT =Ts-Tr is rather arbitrary, the DTA curves are usually marked
with endo or exo direction.

It is essential that reference sample must not undergo any change in state over the
temperature range used and both the thermal conductivity and heat capacity of reference
must be similar to those of samples. Both sample and reference materials should be also
inert towards sample holder or thermocouples. Alumina and silicon carbide are most

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commonly used standard reference samples. DTA profiles are affected by heating rate,
sample size and thermocouple position within the sample.

Exo peak

ΔT=Ts-Tr

Endo peak

Tr
Fig. 10. Typical exo and endo peak in a DTA profile.

Application

Any change associated with enthalpy change can be studied by DTA. In general, DTA
curves are used to get information about temperature and enthalpy changes for
decomposition, crystallization, melting, glass transition etc. In solid catalysis, it is
particularly useful to detect phase changes associated with calcination process. For
example, change of aluminum hydroxide to alumina can be easily detected by DTA.

Book References

• G. Ertl, H. Knozinger and J. Weitkamp, Handbook of Heterogeneous Catalysis,


Vol. 2,WileyVCH, 1997.
• M.E.Brown , Introduction to thermal analysis : Techniques and application ,
second edition, Springer, 2007
• E.N. Kaufmann (Ed), Characterization of Materials, Wiley –Inter Science ,2003

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Lecture 15

Spectroscopy

Spectroscopy is defined as the study of the interaction of electromagnetic waves with


materials. Spectroscopy is used to gain knowledge about the structure of the material.

A molecule in space can have energies in various forms; rotational energy, vibrational
energy or electronic energy . These energies of molecules are quantized and a particular
molecule can exist in different rotational and vibrational energy levels. The molecules
can move from one level to another level only by a sudden jump involving a finite
amount of energy.
E2

∆E

E1

Generation of absorption spectrum

Consider two possible vibrational energy state of a molecule, E1 and E2. Transition can
take place between the levels E1 and E2 provided the appropriate amount of energy
∆E = E 2 − E1 can be either absorbed or emitted by the system. If a molecule in state 1
∆E
is subjected to electromagnetic radiation of a single frequency ν1 =
h
(monochromatic radiation, where h is Plank constant),then the energy will be
absorbed from the incident radiation and the molecule will jump to state E2 . A detector
placed to collect the radiation after its interaction with the molecule will show a
decrease in the intensity of frequencyν 1 . If a radiation beam of wide range of

frequencies is used, the detector will show that energy has been absorbed only from the
ν 1 frequency and intensity of all other frequencies are unaffected. This results in an
absorption spectrum.

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Molecular Vibrations

Vibration motion is described as stretching or bending depending on the nature of the


change in molecular shape. Further, vibration motion can be symmetric / antisymmetric.
Wave mechanics implies that any molecule can never have zero vibrational energy, ie.,
atoms can never be completely at rest relative to each other. The harmonically oscillating
molecules can undergo vibrational changes determined by simple selection rules obtained
from Schrödinger equation.

The vibrations of nuclei in a molecule can be characterized with properties of the normal
mode vibration. Nuclei vibrate at the same frequency and in the same phase. Nuclear
motion does not cause rigid body movement (translation) or rotation of molecules. A
molecule vibrates at its equilibrium position without shifting its center of gravity. Each
type of molecule has a defined number of vibration modes and each mode has its own
frequency. Vibration frequency varies with vibration type. The number of normal
vibration modes in a molecule is related to the degrees of freedom in molecular motion.
For N atomic nuclei in a molecule, there are 3N degrees of freedom as each nucleus can
move in x, y or z directions. Among these, three are related to translation of a molecule
along x, y or z direction as a rigid body and three related to rotation of a molecule around
the x, y or z axes as a rigid body. Hence, the total vibration modes of an N-atomic
molecule is 3N − 6 .For a linear molecule , the rotation around the bond axis is
meaningless, considering the nuclei as points in space. Thus, there are only two rotational
degrees of freedom for the molecule and the total vibration modes are 3N – 5.

Types of vibrations in a molecule:

• Stretching vibration
• In-planar bending vibration
• Out-of-planar bending vibration
For polyatomic molecules, the vibrations are complicated. For example, water which is a
non-linear tri-atomic molecule has three allowed vibration as shown in Fig 1 [3N-6 = 3 ;
N is the number of atoms in the molecule. For carbondioxide, a linear tri-atomic
molecule, the number of allowed vibration is 3N-5 = 4. In Fig. 1, these vibrations are

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shown. For CO2 , there are two bending vibrations; one as shown in the figure in which
the atoms moves in plane of the paper and the other in which oxygen atoms moves
simultaneously into and out of the plane is not shown here. These two vibrations are
identical except in directions.

a) O O
O

H H H H H
H

Symmetric stretch Symmetric bend


-1 -1
Antisymmetric stretch
3651.7 cm 1595.0 cm -1
3755.8 cm

b)
O C O O C O O C O

Symmetric stretch Antisymmetric stretch


-1 Bending
1330 cm
-1
2349.3 cm -1
667.3 cm

Fig. 1 : Fundamental vibrations of (a) water molecule (b) carbon-dioxide molecule

Infra red spectroscopy

Energies of infrared radiation correspond to vibrational energies of molecules. IR


spectroscopy is a vibrational spectroscopy as it is based on the phenomenon of absorption
of infrared radiation by molecular vibrations. IR spectroscopy gives information about
the molecular structure of the materials. Both inorganic and organic materials can be
analyzed. Commonly, the vibrational spectroscopy covers a wave-number range from
−1
200 to 4000 cm .

Infrared Activity
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Among the total number of normal vibration modes in a molecule, only some can be
detected by infrared spectroscopy. Such vibration modes are referred to as infrared active.
To be infrared active, a vibration mode must cause a change of dipole moment in a
molecule.
When a molecule has a center of positive charge and a center of negative charge and if
these two centers are separated by a distance (l), the dipole moment (μ) is defined as
m = el where, e is amount of electrical charge. Mathematically, the
requirement of infrared activity is that the derivative of dipole moment with respective to
the vibration is not zero.

 ∂m 
 ∂q  ≠ 0 where , q = magnitude of normal vibration
  q =0
Species with polar bonds, such as CO, NO or OH exhibits strong IR bands. Covalent
bond or non-polar bonds such as C-C, – C≡C, C=C, N=N, H2 or N2 absorb IR weakly or

not at all.

Further for polar bonds, in case of symmetric stretching if there is no change in dipole
moment, the corresponding vibration will be IR-inactive. But asymmetric stretchings
which are associated with change in dipole moment are always IR-active. As a guideline
following can be used

◦ Symmetric stretch: No change in dipole moment so not IR-active


◦ Asymmetric stretch : Change in dipole moment so IR-active

Analysis by infrared techniques

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IR radiation in the range 4000-400 cm-1 is used to excite stretching and bending
molecular vibrations. Stretching vibrations are of highest frequency and most relevant to
catalyst studies. A complex molecule is likely to have large a number of vibrations.
Normal vibrations are classified in two groups :

1. Skeletal vibrations : In these vibrations all atoms undergo approximately the same
displacement.
Vibration of the carbon chain in organic molecules, which falls in 1400-1700 cm-1
range, is an example.

Fig. 2 : Examples of skeletal vibrations in hydrocarbons

2. Group vibrations: In some vibration modes, displacement of a small group of


atoms may be much more vigorous than those of the remainder. These are called group
vibrations. Group vibration frequencies are almost independent of the structure of the
molecule as a whole and generally fall in the region well above or well below the
skeletal mode.

Vibrations of light atoms in terminal groups, such as –CH3,-OH, -C≡N, >C=O, are of
high frequencies, while vibrations of heavy atoms such as -C-Cl, -C-Br, metal-metal
etc. are of low frequencies. These vibrations fall in this category. Table 1 shows the
stretching frequencies of some molecular groups.

Overall IR spectrum can be broadly divided in five regions :


– X-H stretch regions ( 4000-2500 cm-1) e.g – CH, NH, OH vibrations
– Triple bond regions 2500-2000 cm-1 ; e.g C≡C (2100-2200) C≡N (2240-2280)
– Double bond region 2000-1500 cm-1 ; e.g C=O (1680-1750) C=C (1620-1680)
– fingerprint regions 1500-500 cm-1 ; Single bonds C-N, C-O,C-S, C-Cl etc.
– Metal adsorbate region 450-200 cm-1 e.g M-X ; X= C,O,N
Table 1. Stretching frequencies of some molecular group

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Group Approximate Group Approximate Group Approximate

stretching stretching stretching

frequency frequency frequency

cm-1 cm-1 cm-1

O-H 3600 C=O 1750-1600 -SH 2580

-NH2 3400 C=C 1650 C-F 1050

≡CH 3300 C=N 1600 C-Cl 725

=CH2 3030 C=S 1100 C-Br 650

-C≡C- 2220 -C≡CN 2250 C-I 550

Working principle and instrumentation


An FT-IR instrument uses a system called an interferometer to collect a spectrum. The
interferometer consists of a source, beam-splitter, moving mirror, fixed mirror and
detector.
The energy goes from the source to the beam-splitter which splits the beam into two
parts.
While one half is transmitted to a moving mirror, the other half is reflected to a fixed
mirror.
The moving mirror moves back and forth at a constant velocity. The two beams are
reflected back from the mirrors and recombined at the beam-splitter. The beam from the
moving mirror travels a different distance than the beam from the fixed mirror.

Moving mirror

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Beam splitter
IR source
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Fig. 3. Schematic diagram of FT-IR interferometer

Consequently, an optical path difference (δ) is introduced by the change in the position
of moving mirror. When the reflected beams are combined, few of the wavelengths
recombine constructively while others destructively creating an interference pattern.
Two split beams will show constructive and destructive interference periodically, with
continuous change of δ value. Completely constructive interference occurs when δ = nλ,
but completely destructive interference occurs when δ = ( 1/2+ n)λ. A plot of light
interference intensity as function of optical path difference is called an interferogram.
This interferogram then goes from the beam-splitter to the sample, where some energy is
absorbed and some is transmitted. The transmitted portion reaches the detector. The
interferogram received is converted into a spectrum by using an algorithm called a
Fourier transform using a computer. Fourier transform algorithm transfers information
between a function in the time (t) domain and its corresponding one in the frequency (ω)
domain.

Optical path difference can be considered to be in the time domain because it is obtained
by multiplying time with the speed of a moving mirror. Wave-number can be considered
in the frequency domain because it is equal to frequency divided by the light speed.

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Thus, Fourier transformation converts an interferogram ( intensity vs optical path


difference ) into an infrared spectrum (intensity versus wavenumber)
FT-IR plot
A reference or “background” single beam is also collected without a sample and the ratio
of sample single beam to the background single beam is expressed as a transmittance
spectrum. This transmittance spectrum can be converted to absorbance by using the
relation A = − log T . The x-axis of the FT-IR spectrum is typically displayed in “wave-
-1
numbers” or cm .

Application
In heterogeneous catalysis, IR spectroscopy is used to :
– Study the molecular structure of catalysts
– Identify adsorbed species or adsorbed reaction intermediates and their structures on
catalysts
– Provide information on the nature of acid – basic sites present on catalysts surface
during preparation and reaction

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Examples
1. Identification of bonds :
Fig 4 shows the IR spectrum of alumina. In alumina, the vibrations of OH, Al-OH, and
Al-O bonds generate the observed bands in the infrared region. The stretching vibration
of the OH gives a very intense broadband at 3448 cm-1 whereas their bending vibration
generate band at 1624 cm-1. The band at 1523 cm-1 may be attributed to stretching
vibrations of Al-OH bond. The low-energy region of alumina spectrum shows a broad
band at 500-1000 cm-1, probably produced by vibrations of Al-O bonds.

Fig. 4. IR spectrum of alumina

2. Identification of acid sites


Acid sites can be Lewis acids sites that accept electrons or Bronsted acids sites that
donate proton. In this method, basic molecular probes are adsorbed on the surface acid
sites for identification. Generally, pyridine (C5H5N) which can adsorb on both Lewis and
Bronsted acid sites is used as the probe molecule. Pyridine hydrogen bonded at Bronsted
acid sites gives IR bands at 1485-1490 and 1580-1600 cm-1 over zeolite catalysts whereas
IR bands for pyridine coordinated to Lewis sites gives peaks at 1450 and 1620 cm-1.

Book reference

• Colin N. Banwell & Elaine M. McCash ,Fundamentals of molecular spectroscopy,


Tata McGraw-Hill Pub. Co. Ltd., 2000.
• Y. Leng, Materials Characterization: Introduction to microscopic and spectroscopic
methods, John Wiley & Sons, 2008
• Sam Zhang, Lin Li, Ashok Kumar , Materials Characterization Techniqes, CRC
Press, 2009

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Lecture 16

Raman spectroscopy
Raman spectroscopy is used to analyze the internal structure of molecules and crystals. It
is based on scattering phenomenon of electromagnetic radiation by molecules. Scattering
by molecules can be elastic or inelastic.

 Elastic scattering : the scattered light has the same frequency as that of the source
radiation. Elastic scattering is called Rayleigh scattering.
 Inelastic scattering: the scattered light has a different frequency from that of the
source radiation. Inelastic scattering is called Raman scattering.
Basic process

At room temperature, most molecules are present in the lowest energy vibrational level.
When a material is irradiated with intense electromagnetic radiation of single frequency it
interacts with the molecule and distorts (polarize) the electron cloud around the nuclei to
form a short-lived high energy state, called ‘virtual state’. Energies of these virtual states
are determined by the frequency of the light source used. These high energy virtual states
are very unstable.

Raman Stokes scattering : During inelastic (Raman) scattering ,the molecule returns
from the virtual state to a higher energy level compared to the initial stage (Fig. 1c). A
fraction of photon energy is absorbed by the molecules to remain in the higher energy
vibrational state, V=1 where EV=1 > EV=0 and EV=0 is the ground vibrational state.
Consequently, energy of the reradiated photon is less than that of incident photon. This
type of inelastic scattering is called Stokes scattering.

Raman anti-Stokes scattering : Due to thermal energy, some molecules may be present
initially in the excited state, V=1. If after interaction with the incident light, the molecules
from virtual state return to ground state, V=0, then the energy of the reradiated photon
will increase by the amount of ΔE = EV=1- EV=0 as shown in Fig. 1a. This type of Raman
scattering is called anti-Stokes scattering and involves transfer of energy to the scattered
photon.

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When the electrons excited from ground energy level returns back to ground state V=0
then it corresponds to Rayleigh scattering (Fig. 1b)

Relative intensities of Stokes & anti-Stokes scattering


Relative intensities of these two processes depend on the population of the various states
of the molecule. At room temperature, majority of molecules are expected to be initially
in the ground energy state and excited vibrational state will be small. Consequently, anti-
Stokes scattering will be weak compared to Stokes scattering. Usually in Raman
scattering, Stokes scattering is recorded. As temperature rises, anti-Stokes scattering will
increase relative to Stokes scattering.
Virtual states
a b c

V=1
V=0
anti-Stokes(a) Rayleigh (b) Stokes (c)

Fig. 1. Different transitions observed in Raman process

Raman Activity
To be Raman active, a vibration mode must cause polarizability changes in a molecule.
Mathematically, Raman activity requires that the first derivative of polarizability (α) with
respect to vibration at the equilibrium position is not zero.

The ‘q’ is the displacement of the atoms form equilibrium position. Polarization of
molecules varies with directions in a three-dimensional space. For example, in a linear
molecule such as CO2, the electron cloud has the shape of an elongated ellipsoid that is
more deformable along its long axis than the directions perpendicular to the long axis.

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Generally, if the ellipsoid changes its size, shape and orientation with vibration, that
vibration is Raman active. For example, in case of H2O molecule, all normal mode
vibrations, as shown in Fig.1a , are Raman active because the ellipsoid changes size,
shape or orientation in all cases.
Table 1. Comparison of Infrared absorption and Raman scattering

Infrared spectroscopy Raman spectroscopy


Range of IR frequencies interacts with Intense radiation of single frequency
sample interacts with sample
From incident radiation ,certain frequencies Radiation interacts forming unstable high
are absorbed and loss of these frequencies energy ‘virtual state’ and the photons are
from incident radiation is detected. quickly re-emitted. Re-emitted photons of
different energies are detected
Occurs when incident radiation energy Do not require matching of the incident
match with the energy difference between radiation to the energy difference between
the ground and excited states. the ground and excited states.
To be IR active, a vibration mode must To be Raman active, a vibration mode must
cause dipole moment changes in a molecule. cause polarizability changes in a molecule.
Uses radiation energy comparable to the Uses much higher energy radiation
fundamental vibrations of most chemical compared to the fundamental vibrations of
bonds or systems of bonds most chemical bonds or systems of bonds
Measure frequency of absorbed light Measure the change of frequencies of the
scattered light. Intensity of the Raman
scattered component is much lower ; hence
highly intense light source and a very
sensitive detector are required

Selection rule
Intense Raman scattering occurs from vibrations which cause a change in the
polarizability of the electron cloud around the molecule. Usually, symmetric vibrations
cause the largest changes in polarizability and give the greatest scattering. In contrast for
infrared absorption, the most intense absorption is caused by a change in dipole and
hence asymmetric vibrations which cause this are the most intense. The two techniques
usually give quite different intensity patterns. As a result, the two are often
complementary and used together to give a better view of the structure of a molecule. In

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some cases, vibrations of a molecule can be both infrared and Raman active. Selection
rules related to symmetry is :
 Rule of thumb: symmetric=Raman active, asymmetric=IR active

Table 2. Raman and IR active band of CO2 and H2O molecule

CO2 H2 O

Symmetric stretch Raman active: Symmetric stretch Both Raman and


1335 cm–1 IR active : 3652
cm–1

Antisymmetric IR active: 2349 Antisymmetric Both Raman and


stretch cm–1 stretch IR active : 3756
cm–1

Symmetric bend IR active : 667 Symmetric bend Both Raman and


cm–1 IR active : 1596
cm–1

Working principle and instrumentation


A typical Raman system consists of the following basic components:

1) An excitation source, usually a laser

2) Sample illumination system and light collection optics

(3) Double or triple monochromator /Wavelength selector

(4) Signal processing system consisting of a detector, an amplifier, and an output device.

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Sample is mounted in the sample chamber and laser light is focused on it with the help of
a lens. The scattered light is collected using another lens and is focused at the entrance
slit of the monochromator. The width of the monochromator slit is set for the desired
spectral resolution. Monochromator effectively rejects stray light and serves as a
dispersing element for the incoming radiation. Light leaving the exit slit of the
monochromator is collected and focused on the surface of a detector. This optical signal
is converted to an electrical signal within the detector. Signal is processed in a computer
to develop the final spectrum. Schematic diagram of Raman spectrophotometer is shown
in Fig. 2.

Laser Sample cell

Lens

Monochromator unit Detector

Fig. 2. Schematic diagram of Raman spectrophotometer

The major problem associated with Raman spectroscopy is the very weak intensity of the
scattered light. Consequently, it requires an extremely monochromatic high-energy light
source, very effective filtering of Stokes scattering and very high sensitivity of the
detecting device. Excitation source must be strong enough to generate sufficient Raman
signals and monochromatic to provide clean and uncomplicated spectra. A laser typically
is used as the excitation source because it can provide a coherent beam of monochromatic
light with high intensity. Different laser beams in ultraviolet (UV), visible (Vis) or near
infrared (NIR) range are used. Argon and krypton ion laser sources, being more intense,
give better spectra and are the most commonly used. Light scattered from a laser excited
sample is collected with a lens and is sent through filters to a monochromator. Raman
scattering is effectively separated from Rayleigh scattering by multiple monochromators
. At present, various arrangements such as notch filters, tunable filters, laser stop
apertures, double and triple spectrometric systems are used to reduce Rayleigh scattering

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and obtain high-quality Raman spectra. Types of detectors mainly used are
photomultiplier tube, photo diode array or charge coupled device.

Sample preparation

Raman analysis require no special sample preparation. All kind of samples in the form of
liquid, solid or gas can be analyzed. Short measuring time, normally a few seconds, is
required to obtain a Raman spectrum.

Applications

Raman shift provides information about vibrational, rotational and other low frequency
transitions in molecules. It is used for the qualitative study of molecular structures. It is
generally not used for quantitative studies, since due to weak Raman scattering,
sensitivity is low.

Raman spectroscopy is complementary to IR spectroscopy. IR and Raman both are useful


for Fingerprinting.

Examples

1. Raman spectra of titania and zirconia


The Raman spectra of titania and zirconia samples are shown in Fig. 3.

ZrO2
TiO2
Intensity

Intensity

0 500 1000 1500 2000


0 500 1000 1500 2000
-1
Raman shift cm Raman shift cm -1

Fig. 3. Raman spectra for titania and zirconia

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2. Study of surface vanadia species


The surface structure of supported vanadium oxide species can be studied using Raman
spectroscopy. Different types of surface vanadium species are observed as shown in Fig
4. Isolated V = O and polymeric V = O gives Raman band at 1026 cm-1 and 1009 cm-1,
respectively.

Isolated V=O Polymeric V=O

V V V

SUPPORT

Fig. 4. Various surface vanadia species observed on supported vanadia catalysts

Book reference

• Colin N. Banwell & Elaine M. McCash ,Fundamentals of molecular spectroscopy,


Tata McGraw-Hill Pub. Co. Ltd., 2000.
• Ewen Smith & Geoffrey Dent, Modern Raman Spectroscopy – A Practical
Approach, John Wiley & Sons Ltd. 2005
• Y. Leng, Materials Characterization: Introduction to microscopic and spectroscopic
methods, John Wiley & Sons, 2008

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Lecture 17
Electron Microscopy

Microscope forms an enlarged image of the original object in order to convey its internal
or external structure. The magnification and resolution of microscope is given as

(a) Magnification = objective lens × eyepiece lens


(b) Resolution (rd) is defined as closest spacing of two points which can be clearly seen
through the microscope as separate entities. Resolution can be determined as :

0.61 l 0.61 l
=rd =
m sin α NA

l = wavelength of light
m = refractive index of the medium between the object and objective lens
α = the half angle made by aperture at the specimen
NA = m sin α = numerical aperture

By increasing the dimension or by employing large number of lenses, the magnification


can be increased, while shorter wavelength yields higher resolution.
Electrons are considered as radiation with wavelength in the range 0.001 - 0.01 nm
compared to 400- 700 nm wavelength of visible light used in an optical microscope. In an
electron microscope, a focused electron beam is used instead of light to examine objects,
and the image of the specimen is obtained on a very fine scale. Because of the use of
large number of lenses and electrons of very low wavelength, magnification and
resolution for electron microscopes is much higher. High magnification and resolution
makes electron microscopes extremely useful for revealing ultrafine details of material
microstructure. Optical microscopes have a maximum magnification power of 1000, and
resolution of 0.2 μm compared to resolving power of the electron microscope that can
reach 1,000,000 times and resolution of 0.2 nm. Hence, electron microscopes deliver a
more detailed and clear image compared to optical microscopes.

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 Two main types of electron microscopes


• Transmission electron microscopes (TEM)
• Scanning electron microscopes (SEM)
Transmission Electron Microscopes (TEM)

The optics of the TEM is similar to conventional transmission light microscope. It was
developed in the 1930s. It is capable of displaying magnified image of thin specimen
3 6
with magnification in range of 10 to 10 . Information that can be obtained using TEM
include :

• Topography : surface features , texture


• Morphology : shape and size of the particles
• Crystallographic arrangement of atoms
• Composition : elements and the their relative amounts

Interaction of electron beam with sample

Interaction of electron beam with the sample results in three types of electrons :

i. Unscattered electrons: These are electrons that are transmitted through the thin
specimen without any interaction with the sample. Transmission of unscattered
electrons is inversely proportional to the specimen thickness. The areas of
specimen that are thicker will have fewer transmitted unscattered electrons and
will appear darker. Conversely, thinner areas will have more transmitted electrons
and will appear lighter.

ii. Elastic scattered electrons: These are incident electrons that are scattered by the
atoms of the specimen in an elastic fashion; that is without any loss of energy of
electrons. The elastically scattered electrons form a pattern that yields information
about the orientation, atomic arrangements and phases present in the area being
examined.

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iii. Inelastic scattered electrons : Incident electrons that interact with the specimen
atoms in an inelastic fashion and lose energy during the interaction, fall in this
catagory. The extent of loss of energy by incident electrons depends on the
characteristic of interacting elements and is used to study the compositional and
bonding (i.e. oxidation state) information of specimen region being examined.

Working Principle and Instrumentation

The Fig. 1 shows the arrangement of components for transmission electron microscope.
An electron gun at the top of the microscope emits electrons that travel through vacuum
in the microscope column. Vacuum is essential to prevent strong scattering of electrons
by gases. Electromagnetic condenser lenses focus the electrons into a very thin beam.
Electron beam then travels through the specimen and then through the electromagnetic
objective lenses. At the bottom of the microscope, unscattered electrons hit the
fluorescent screen giving image of specimen with its different parts displayed in varied
darkness, according to their density. The image can be studied directly, photographed or
digitally recorded.

Electron source
Electron beam

Condenser lens
Microscope column

Sample
Vacuum

Objective lens

Screen

Fig. 1. Schematic diagram illustrating transmission electron microscope

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A transmission electron microscope has the following components along its optical path:
1. Electron source
2. Condenser lens
3. Specimen stage
4. Objective lens and projector lens
5. Screen/photographic film/CCD camera

In the electron gun, electrons are emitted from the surface of the cathode and accelerated
towards the anode by a high voltage (Vo) to form a high energy electron beam. All lenses
in the electron microscope are electromagnetic. Charged electrons interact with the
magnetic fields and magnetic force deflects or focuses an electron beam. The condenser
lens system controls the beam diameter and convergence angles of the beam incident on a
specimen.

Sample preparation

Preparation of specimens is the most tedious step in TEM. To make the material
electronically transparent, material thickness is limited. Specimens have to be prepared
with thickness of ~ 100 nm. For higher atomic weight material, the specimen has to be
thinner. TEM sample preparation depends on type of materials used.

For bulk material, TEM specimen preparation is done in two steps :

◦ Pre-thinning : thinning to 0.1 mm thickness


◦ Final-thinning: thinning to 100 nm thickness
Pre-thinning :In pre-thinning stage, specimen less than 1mm thick is prepared by
mechanical cutting (with a diamond saw). Then, a 3-mm-diameter disc is cut using punch
before further reduction of thickness. Grinding is most commonly used to reduce the
thickness of metal and ceramic specimens.

Final thinning :Final thinning is mainly done by electrolytic thinning & ion milling,
which create a dimpled area on pre-thinned specimens that have regions of electron
transparency as shown in Fig.2. In electrolytic thinning, metal specimen is made the
anode in an electrolytic cell. On passing current, the metal is gradually dissolved and

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deposited on the cathode. Finally tiny holes appear, the edge of which are suitable for
electron transparency. In ion milling method, samples are bombarded with a beam of
energetic ions to reduce the thickness by knocking atoms out of the specimen. This
method can also be used for ceramics and other non-conducting materials. For polymeric
and biological specimens, ultramicrotomy method is used where specimen is cut into thin
sections by a cutting tool such as glass knife or diamond knife.

3 mm

Electron transparent zone


Dimpled area

Fig.2 . Thinning of bulk specimen for TEM analysis

For powder samples, such as catalysts, the powder size is reduced by grinding, to a very
fine size till the particle thickness is small enough to allow electron transmission. These
fine particles are then suspended in a volatile solvent such as isopropanol. A drop of this
particle suspension is placed on a thin carbon foil supported by a conventional
microscope grid. On evaporation of solvents, the powder particles are ready for
observation. Alternatively, the powders can be embedded in some suitable matrix such as
epoxy resin or metals, from which a flat sheet of 3 mm diameter is cut out to study by
conventional methods.
Magnification and resolution
Magnification and resolution is defined in the same way as for transmission light
microscope.
 Magnification of any convergent lens M is given by
v− f
M=
f

f = focal length of lens ;v = distance between image and lens

 Resolution of electron microscope can be written as

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0.61 l
r =
α

α = Angle through which beams are deflected ; λ= wave length of electrons


For λ=0.0037 nm (wave length of 100 kV electrons ) and α = 0.1 radians (~5 degrees)
resolution of ~0.02 nm is obtained

Scanning electron microscope

SEM is most widely used type of electron microscope for study of microscopic structure.
In SEM, image is formed by focused electron beam that scans over the surface area of
specimen. The incident beam in SEM is also called electron probe. The incident beam is
of typically 10 nm diameter in contrast to beam of TEM which is about 1 μm. In SEM,
image is not formed by instantaneous illumination of the whole field as for TEM. SEM is
relatively easy to operate and maintain, compared to a TEM. In TEM, unless specimen is
made very thin, electrons are strongly scattered within the specimen or even adsorbed
rather than transmitted. SEM overcomes this limitation.

Electron sample interactions

The interaction of electron beam with samples results in secondary electrons


andbackscattered electrons that are detected by standard SEM equipment.

Secondary Electrons : As incoming electrons pass through the specimen, they impart
some of their energies to electrons of nearby specimen atom. This causes ionization of the
electrons of the specimen atom and slight energy loss and path change of the incident
electrons. These ionized electrons then leave the atom with a very small kinetic energy
(5eV) and are termed as secondary electrons. The secondary electrons escape from a
volume near the specimen surface, at a depth of 5–50 nm and hence are useful to gain
topography related information.

Backscattered Electrons: Some of the electrons of the incident beam collide with the
specimen atoms that fall in the path and are reflected or back scattered. The production of
backscattered electrons varies directly with the atomic number of the specimen. When
backscattered electrons are detected, higher atomic number elements appear brighter than

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lower atomic number elements. This interaction is utilized to differentiate parts of the
specimen that have different average atomic number.

Working principle and instrumentation

In SEM, there are several electromagnetic lenses, including condenser lenses and one
objective lens. Electromagnetic lenses are for electron probe formation, not for image
formation directly, as in TEM. Two condenser lenses reduce the crossover diameter of the
electron beam. The objective lens further reduces the cross-section of the electron beam
and focuses the electron beam as probe on the specimen surface. Objective lens thus
functions like a condenser. This is in contrast to TEM where objective lens does the
magnification.

Electron Gun
Electron beam
st
1 Condenser lens
Vacuum
nd
2 Condenser lens

Microscope column
Objective lens

Raster Scanning
of Sample Detector

Fig. 3. Schematic diagram illustrating scanning electron microscope

Electron probe or beam is scanned across the specimen and the procedure is known as
Raster scanning. Raster scanning causes the beam to sequentially cover a rectangular area
on the specimen. The signal electrons emitted from the specimen are collected by the
detector, amplified and used to reconstruct the image according to one-to-one correlation

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between scanning points on the specimen and picture points on the screen of cathode ray
tube (CRT). CRT converts the electronic signals to a visual display.

Everhart–Thornley is commonly used detector in SEM. It consists of a scintillated photo


multiplier system. As electrons strike the scintillator, photons are emitted. The photon is
transmitted a light pipe into a photomultiplier tube, which converts the photon into pulses
of electrons, which are amplified and used to modulate the intensity of CRT.

Magnification and Resolutions

Magnification

In SEM, image is not magnified by any lens as opposed to TEM where magnification is
determined by power of the objective lens. Magnification of SEM is determined by the
ratio of the linear size of the display screen to the linear size of the specimen area being
scanned. Raster displayed on the CRT is larger than the corresponding Raster scanned by
the electron beam on the specimen (Fig 4). The linear magnification is given by

side length of CRT [ L]


Linear magnification =
side length of raster [l ]

Raster on CRT

L
Raster on sample

Fig. 4 . Raster on sample and corresponding raster on CRT

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For example, if electron beam is made to scan 10 μm×10 μm raster on the specimen and
the corresponding image raster is displayed on CRT screen as 100mm × 100 mm, then
linear magnification will be

side length of CRT [ L] 100 ×10−3 m


=
Linear magnification = = 10000
side length of raster [l ] 10 ×10−6 m

SEM is able to provide image magnification from about 20× to greater than 100,000× .

Resolutions (Pixels)

Image performance in SEM can be explained on the basis of the picture element or pixel.
The amplified signal from the detector makes a minimum spot size of ~ 0.1 mm or 100
micrometer in the CRT. The spot on the CRT mimics the movement of the electron beam
on the specimen. Therefore for each of the pixels on the CRT, there is a corresponding
100
pixel on the specimen. The size of specimen pixel (p) is given by p = mm where M
M
= magnification

Resolution is defined as the smallest separation of two points that a microscope can
detect as separate entities. In order to resolve two features A and B in Fig 5 they must
occupy separate pixels. Therefore, working resolution of SEM can be no better than the
specimen pixel size ‘p’ as given by above equation.

A
B CRT

A B
Sample

Fig. 5. Raster as array of picture points or pixel on CRT and sample

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Resolution of SEM is also controlled by the size of the electron probe scanning the
specimen. If the electron probe is larger than the specimen pixel, then the signal from
adjacent pixels are merged and the resolution is degraded (Fig 6a).If electron probe is
smaller than specimen pixel, then signal will be weaker and noisy (Fig 6b).For optimum
performance, probe diameter or sampling volume is made equal to the specimen pixel
diameter (Fig 6c).This means that for optimum performance, the probe size should be
adjusted as the magnification of the microscope is altered. However, ultimate resolution
depends on the smallest probe which can provide adequate signal from the specimen.
Incident electron beams
a b c

a b c

Sample pixels
Fig. 6.Size of the electron probe scanning the specimen with respect to specimen pixel.

Sample preparation

Sample preparation for SEM is minimal. This has made SEM more widely used than
TEM which requires a very thin specimen and tedious sample preparation procedure.
Sample preparation for SEM involves only sizing the specimens to fit SEM specimen
holder and removing surface contaminants. This also helps to preserve the surface
characteristics for topographic study.

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Examples

Fig 7 shows SEM image of titania samples prepared by precipitation using TiCl2 as
precursor. The image shows that the prepared titania sample consisted of particles with
wide size distribution and irregular shape. The size of the particles can be measured
manually by using the scale given in the figure or by any image analysis software.
The image part with relationship ID rId273 was not found in the file.

Fig. 7. SEM image of titania samples prepared by precipitation method

Energy dispersive spectrometer (EDS)

In this method, the X-ray generated from interaction of electron beam with sample, is
used for chemical analysis of the sample. As high energy electrons strike the sample
surface, along with secondary and backscattered electrons, characteristic X-rays are
emitted whose wave length depends on nature of atoms in sample. These X-rays can be
used to characterize all type of solid materials. The characteristics X-ray is generated
when an inner shell electron is knocked out of the atom and the vacant site is filled with
electron from outer shell. The excess energy is released and the amount of released
energy, corresponding to X-ray range, is characteristics of the particular atom.
For example, if a K shell electron has been knocked out of a molybdenum atom, and
vacancy is filled by L electron, then ΔE= 17400 eV, is emitted as Kα X-ray of Mo. The

hc
wave length of the corresponding X-ray is =
λ = 0.071 nm . On the other hand if
∆E
vacancy is filled by M shell electron, the difference in energy is ΔE ~ 19600 eV. Then the
corresponding X-ray emitted is Mo K β
, λ = 0.063 nm. The K-series lines are more

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frequently used for analysis. For heavier atoms, the energy required to knockout the K-
shell electron increases and consequently exciting the K series line become difficult. In
these cases L series and M series of lines can be used which are generated by knocking of
L or M shell electrons.

Fig. 8. Emission of X-ray when outer L shell electron fills the K shell electron vacancy

The energy and wavelength of X-rays are different for each atomic species and by
measuring them, the elements present in sample can be detected and quantified. From X-
ray spectrum following analysis can be done:
1. Measurement of wavelength/energy of each characteristics X-ray emitted. It can be
used to determine the elements present in sample. This is a qualitative analysis.
2. Measurement of X-ray of any type emitted per unit time. This corresponds to amount
of the element present in sample. This is quantitative analysis.

SEMs are equipped with an energy dispersive spectrometer or EDS detection system
which is able to detect and display most of the X-ray spectrum. The detector normally
consists of semiconducting silicon or germanium. Since, the X-rays can not be deflected,
the detector has to be placed in line of sight of the specimen. In order to collect as many
X-rays as possible, the detector is placed near the specimen (20 mm or less from the
specimen). It normally occupies a similar position to the secondary electron detector.
Each incoming X-rays to the detector excites a number of electrons into the conduction
band of the silicon leaving an identical number of positively charged holes in the outer
electron shells. The energy required for each of these excitations is only 3.8 eV,

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consequently the number of electron-hole pairs generated is proportional to the energy of


the X-ray photon being detected. For example, an Al K X-ray having energy of 1.49 keV,
α

will give rise to approximately [(1.49 × 1000) eV/3.8 eV] = 392 electron hole-pairs. If
voltage is applied across the semiconductor, a current will flow as each X-ray is absorbed
in the detector and the magnitude of the current will be exactly proportional to the energy
of the X-ray. The current which flows between the electrode when an X-ray enters the
detector lasts for an extremely short time, less than 1 µs and is normally referred as pulse.
Each pulse is amplified and stored in a computer. The EDS spectrum of alumina is shown
in Fig 9. It shows the peak due to Al and O.

keV

Fig. 9 EDS spectra of alumina

Book reference

• P.J. Goodhew, J. Humphreys ,R. Beanland, Electron microscopy and analysis , 3rd
ed.,Taylor & Francis, 2001
• Y. Leng, Materials Characterization: Introduction to microscopic and spectroscopic
methods, John Wiley & Sons, 2008

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Lecture 18

Reactor types and catalysts test

Reactor types

Reactors can be classified based on different criterion such as size, reactor material,
methods of charging and discharging or type of fluid flow. For fluid – solid
heterogeneous system reaction rate is based on mass of solid catalyst rather than on
reactor volume. In laboratory scale, the reactions are carried out in micro reactors with
diameters ranging from 1 – 5 mm for testing up to 0.1 – 1gm of catalysts. In industry,
diameter and height of reactors can vary from 1 to 10 m and 2 to30 m respectively. The
reactor materials also vary depending on usage. Laboratory reactors are usually made of
glass, quartz or stainless steel with few mm wall thicknesses. The large industrial reactors
depending on usage are usually made of mild steel or stainless steel or other alloys. The
wall thickness can range from of 6-15 mm depending on process pressure. Depending on
the operation, reactor can be batch, mixed flow or packed bed type. The choice of reactor
depends on the type of reaction. For examples, many hydrogenation reactions are carried
out in CSTR while many of the solid catalysts are tested in packed bed reactor. Reactor
selection also depends on the type of catalyst and its activity, selectivity and deactivation
behavior. The schematic diagram of different type of reactors is shown in Fig 1.

For study of catalytic reactions in laboratory different reactors are used. For example
fluid-solid catalytic reactions are studied in (1) packed bed reactors heated in furnace, (2)
Carberry reactors equipped with rotating catalyst basket and cooling or heating jacket or
(3) Berty reactor with internal circulation and cooling or heating jacket. For reactions
involving gas-liquid-solid, slurry CSTR with cooling or heating jacket or packed bed
reactor with downflow, upflow or countercurrent flow of gas and liquids are used.
Laboratory reactors are mainly used for measuring reaction kinetics and catalyst activity
at different conditions of temperature and pressure.

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Fixed bed reactor

The fixed bed or packed bed reactors are most commonly used for study of solid catalyst.
A fixed bed reactor usually consists of a cylindrical vessel packed with catalyst pellets
and easy to design and operate. The metal support grid and screen is placed near the
bottom to support the catalyst. Inert ceramic balls are placed above the catalyst bed to
distribute the feed evenly.

Advantages of packed bed or fixed bed reactor include ideal plug flow behavior, lower
maintenance cost and reduced loss due to attrition and wear. Heat management is very
important aspect for design of fixed bed reactor. Poor heat distribution may result in non
uniform reaction rates and consequently low reactant conversion. Poor heat transfer may
also result in generation of hot spots and thermal degradation of catalyst. However, the
situations are observed more in large fixed bed and for highly exothermic or endothermic
reactions when temperature control is difficult. The regeneration or replacement of
catalyst is also difficult in fixed bed reactors and process needs to be shutdown. Another
major disadvantage of packed bed reactor is plugging of bed due to coke deposition
which results in high pressure drop. High pressure drop is also observed for small beads
or pellets of catalysts. However, increase in pellet size increases the pore diffusion
limitation.

Catalyst pellet sizes are usually in the range of 1 to 10 mm. Non-uniform packing of
catalysts can cause channeling of fluids leading to poor heat and mass transfer. The
column to particle diameter is maintained in between 10 to 20 to minimize channeling.
The bed voidage is usually 70 to 90 %. Plug flow behavior is ensured by maintaining
ratio of reactor length to catalyst particle diameter greater than 50. The allowed pressure
drop is less than 0.5 inch water per foot of bed depth. Usually the ratio of bed height to
diameter is maintained greater than 0.5.

For better heat management for very highly exothermic (or endothermic) reaction the
multitubular reactor is used with catalyst packed inside the tubes. The cooling (or
heating) fluid flows through the shell side. The length is limited by allowable pressure
drop. The multitubular reactor has high surface area for heat transfer per unit volume. For

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determination of heat transfer and mass transfer properties several correlations are
available in literature.

Fluidized bed reactors

In fluidized bed reactor catalyst pellets of average size less than 0.1 mm are fluidized by
the reactant fluid. The linear velocity is maintained above the minimum fluidization
velocity required to obtain the fluidized bed. As the superficial velocity increases, the bed
expands and become increasingly dilute. At high enough linear velocity, the smallest
catalyst particles escape from the bed and have to be separated from exhaust gases and
recycled.

In fluidized bed, heat transfer is much better resulting in more uniform temperature
compared to packed bed reactor. Frequent regeneration of catalyst can be done without
any shutdown of the process. However, fluidized bed is a complicated system to operate
and requires extensive investments and high operating and maintenance cost. Other major
disadvantages are attrition and loss of catalysts due to fluidized condition. Modeling of
fluidized bed flow is complex. The fluidized bed is assumed to consist of bubble and
emulsion phases which can be modeled respectively by plug flow and CSTR, as the
emulsion phase is assumed to be well mixed. Correlation for heat and mass transports are
available in literature. The reactor is extensively used for catalytic cracking process.

Carberry reactor or Berty reactor

For catalytic investigations, reactors equipped with rotating basket or fixed basket with
internal circulation can be used. These CSTR type reactors are used to minimize the
inherent mass and heat transfer limitations observed in fixed-bed reactors. These reactors
are frequently used in industry to evaluate reaction mechanism and reaction kinetics. The
most common type of reactors used are Carberry and the Berty reactors.

The main feature of the Carberry reactor is that the catalyst particles are contained
in a spinning basket or embedded in the blades of a spinning agitator. The mounted
catalyst is rapidly rotated resulting in good mixing between reactants in fluid phase and

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the solid catalyst. This minimizes the mass transfer and heat transfer resistances. The
basket or impellers can spin up to 2,500 rpm.

The Berty reactor uses an internal recycling to achieve perfectly mixed behavior. The
catalyst is contained in a fixed bed basket through which the reacting gases circulate.
The catalyst basket is equipped with large diameter impellers rotated in order to circulate
gases & liquids past solid catalysts. An internal recirculation rate of 10 to 15 times of the
feed rate effectively eliminates external diffusion resistance and temperature gradient.
Retaining the solid catalyst in a spinning woven wire mesh basket allows gas / liquid
circulation with low pressure drop. Circulating the reactants past the catalyst minimize
wearing & breakage.

Multiphase reactors

Slurry reactors

The catalytic reaction can also be carried out in two–phase or three –phase stirred tank
reactors also known as slurry reactors. In three –phase reactor, gas and liquid reactants
are brought into contact with solid catalyst particles. In two–phase reactor, fluid phase is
usually liquid reactant in contact with the solid catalyst. The reaction of gaseous reactant
with catalyst is usually carried out in fixed bed reactor. In three –phase slurry reactor the
gaseous reactant and solid catalysts are dispersed in continuous liquid phase by
mechanical agitation using stirrer. The efficient stirring ensures nearly uniform
composition throughout the reactor. This kind of reactor is used in hydrogenation,
oxidation, halogenations and fermentation process. The advantages include nearly
isothermal operation and good heat and mass transfers. The use of powder catalysts
having high activity minimizes the intraparticle diffusion limitation. The reactors can be
operated in batch, semi batch or continuous mode. In three – phase system bubbles of gas
rise through agitated slurry. Solid particles are in size range of 0.01to 1.0 mm. The solid
concentration can be up to 30 vol. %. Lower concentration is also used. In hydrogenation
of oil with nickel catalyst, the solid content is 0.5 vol. %. The external transport effects
are important in slurry reactors and details are discussed in lecture no. 30. Hydrogenation
of oils is carried out in slurry of nickel catalyst particles. Industrial hydrogenation

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reactors are usually of the size in the range of 500-200 L. The reactors are operated up to
pressure of 200 atm and temperature of 350 0C. The reactors are equipped with internal
agitator, gas inlet, facility for insitu sampling and heater or cooler for temperature
control.

Trickled bed reactors

In trickled bed reactor gaseous and liquid reactants flow co-currently downward over a
packed bed of solid catalyst particles. The liquid is distributed across the reactor cross
section by a distributor plate. The gas enters at the top and distributed along with the
liquid. The liquid flows downward by gravity and drag of the gas. For low liquid flow
rates and low to moderate gas flow rates, the gas phase is continuous with liquid trickling
down forming film over the solid catalyst. The thickness of the liquid film has been
estimated to vary between 0.01 and 0.2 mm. This flow regime is known as a trickle flow
regime. The fluid approaches plug flow leading to higher conversion than slurry reactors
for the same reactor volume. Other advantages include ease of installation, minimal
catalyst handling and low catalyst attrition as in packed bed reactor. Disadvantages
include maldistribution of flow resulting in channeling or bypassing, possibility of non
uniformity in packing, incomplete contacting or wetting and intraparticle diffusion
resistance. Catalyst bed depth is limited by pressure drop, catalyst crush strength and
maximum adiabatic temperature increase for stable operation. The reactor length to
diameter ratio can vary between 1 and 10 depending on the allowable pressure drop.
Other parameters important for trickled bed include void fraction of bed, holdup for
phases, wetting efficiency (fraction of catalyst wetted by liquid), gas – liquid mass
transfer coefficient, liquid–solid mass transfer coefficient, liquid and gas mixing, pressure
drop and heat transfer coefficients. The wetting efficiency of the catalyst is important for
reaction rate and increases with increasing liquid rate. The trickle bed reactor is most
commonly used for hydrogenation and hydrodesulfurization reactions.

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Bioreactors

In bioreactor live cells or enzymes are used as catalyst to perform the biochemical
reactions. Bioreactor operations are limited by the conditions favorable for the biological
systems. Most living cells can tolerate only mild conditions of temperature and pH.
Hence in bioreactors stringent control of temperature, pH or any contamination is needed.
Bioreactor may have two phases, liquid-solid as in anaerobic process or three phases, gas,
liquid and solid as in aerobic process. The solid phase typically contains the cells
(bacteria, fungi, algae etc.) that serve as biocatalyst. The density of biocatalytic phase is
close to water. The biocatalyst can also be used in immobilized form in which cells are
trapped within solid or semi solid structure such as porous particles or gel. Liquid is
primarily water with dissolves the feed and products. In aerobic bioreactor the gas phase
consists of primarily air and product gas CO2. Bioreactors are mainly operated in batch
or semi batch mode allowing better control of process parameters. Increasing number of
bioreactor is operated in continuous mode such as in wastewater treatment, lactic acid
production, production of human insulin etc.

a) Carberry reactor b) Berty reactor

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c) Packed bed reactor d) Multi tubular reactor e) Fluidized bed reactor

g) Agitated slurry reactor f) Trickled bed reactor

Fig. 1. Schematic diagram of different type of reactors

Catalyst tests

Activity and selectivity

The performance of catalyst is characterized by its activity for reaction and selectivity for
a product. The activity of a catalyst for a reaction at specified conditions is generally
expressed in terms of rate of reaction at that condition over the catalyst. The catalyst that
shows higher rate of reaction at the given conditions is said to have higher activity. For
solid catalyzed reaction, rate can be defined as, r = g mol of reacted /s. g of catalyst.
Here mass of solid is used because amount of catalyst is important. The reactor volume

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that contains the catalysts is of secondary importance. Activity is also expressed in terms
of conversion of a reactant achieved. Higher the conversion at given conditions, higher is
the activity of the catalyst for that reaction. The conversion can be defined as follows

Moles of reactant in inlet stream- Moles of reactant in outlet stream


Conversion (%) ×100
Moles of reactant in inlet stream

For supported metal catalysts, defining activity in terms of metal sites is more useful as
the metal sites actually act as the active sites for chemical reactions. Hence, activity is
often expressed in terms of turnover frequency or TOF. TOF is defined as the number of
molecules reacting per active site per second (s-1). Though the TOF value is expected to
be constant for a particular metal catalyst for a given reaction at specified conditions,
however, in reality significant difference may be observed due to differences in catalyst
preparation, metal support interaction, crystallite size, surface structure and morphology
etc.

Total no. of molecules reacting


TOF = s −1
total no. of metal sites × seconds

The next important parameter determining the performance of catalyst is selectivity for a
particular product. The selectivity of a product X can be defined in several ways. One of
the definitions is shown below:

Moles of product X
Selectivity of X ( % )
= ×100
Total moles of all products

The performance of catalyst is tested in a suitable experimental setup. Fig. 2 shows a


schematic diagram of a simple experimental setup for studying gas phase reaction over
solid catalysts. Typically, solid catalysts are tested in a tubular down-flow reactor. A
simple manometer or any pressure gauge can be included before the reactor to ensure that
the pressure drop is within acceptable limits. All the reactants are combined in a mixer
and sent to the reactor where it comes in contact with the catalyst bed. The product gases
or liquids are usually analyzed using a gas chromatograph equipped with suitable

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columns. The columns are selected so that the product compounds are separated
efficiently giving distinct peaks that can be easily identified and quantified. Further
detector type and temperature as well as carrier gas type and flow rates are also important
parameters determining the retention time and peak area in a chromatograph. Catalytic
tests are carried out at predetermined range of temperature, pressure, feed composition
and total flow rates depending on reactions. The catalysts amount range to be used is also
fixed according to the requirement.

8
9
3 6
1
5

7
3
11
10
2

1 & 2. Reactant gas cylinders


3. Mass flow controller for control flow or reactant gas
5. Silica gel trap for removing any moisture present in gas mixture
6. Mixer for well mixing of all the reactant gases EXIT
12
7. Manometer to monitor any pressure drop
8. Thermocouple to measure catalyst bed temperature
GC for
9. Thermo well to hold the thermocouple product
10. Quartz reactor holds the catalyst bed analysis
11. Furnace to maintain the reaction temperature

12. Product collector

Fig. 2. Schematic diagram of a typical experimental setup

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2.3.2.1 Collecting data from laboratory reactors

Kinetic data are collected for the following purposes:

– Determination of activity-selectivity and deactivation data for catalyst selection


– Determination of reaction mechanism and kinetic parameters for understanding the
reaction at the fundamental level so the reaction process can be modeled which can be
used for design of reactors.
Investigation of the reaction kinetics is done at steady state conditions for most active and
selective catalyst. The effect of temperature and partial pressures of reactants on the
activity and selectivity is investigated in the desired temperature range. The process of
data collection typically involve three major steps :

1. Selection of a reaction and catalyst


2. Selection of reactor type
3. Analysis of data

Selection of reaction Selection of Selection of Collection Analysis of


and catalysts reactor process of data data

Reactor design and Rate Reaction


process optimization expression mechanism

Fig. 2. Steps for obtaining and analyzing kinetic data

To measure the specific catalytic activity or intrinsic reaction kinetics, the data must be
collected in absence of any pore diffusion limitations, mass transfer limitations or heat
transfer limitations. For analysis of data collected in the presence of mass transfer or heat
transfer limitations, suitable criterion should be included during analysis. Deactivation of
catalysts should be also avoided during data collection. These will be discussed in detail
in later sections. Further data should be collected over a wide range of temperature and
reactant concentrations to provide adequate reaction model that can be applicable at wide
temperature and concentration range.

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Mode of reactor operations

Reactors can be operated in two ways:

1. Integral mode
2. Differential mode
Integral reactors

When a reactor is operated at high conversion, the reactor is said to be an integral reactor.
When reaction takes place in a packed bed reactor at high conversion there is possibility
of wide variation of conversion and reaction rate within the reactor even under isothermal
conditions. Hence, the integral form of design equation is to be used. This is the basis for
design for an ideal packed bed reactor.

x Af
W dX A
FAo
= ∫
0
−rA (1)

Differential reactors

When the reaction in a tubular reactor is carried out at very low conversions, the changes
in conversion and reaction rate across the reactor are small enough to be neglected and
the rate can be considered constant across the reactor. Then the rate in above equation [1]
can be considered constant and taken out of the integral and the equation can be
simplified to

W X
= A
FAo −rA

This above equation is same as for mixed flow reactor or CSTR. In this case analysis of
data is simplified.

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Book Reference

• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981


• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications,2001
• D.W.Green, R.H. Perry, Perry´s chemical engineer´s handbook, 8th Edition,
McGrawHill Company,2007
• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India, 1999
• R. J. Farrauto, C. H. Bartholomew, Fundamentals of Industrial catalytic Processes,
Blackie Academic & Professional, 1997

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Lecture 19

Reaction mechanism and kinetic study

Reaction mechanism and rate equations

For irreversible gas phase reaction A ( g ) → B ( g ) , global rate for catalyst particles is

expressed in terms of temperature and concentration of A in bulk gas stream which can
be measured or specified directly. Global rates of catalytic reactions are usually
expressed per unit mass of catalyst.

Power law model

For homogeneous reaction, power law form of rate equation is used where rate is
function of concentration and rate is determined by fitting data to the equation. The
exponents on the concentration is the apparent order of the reaction and ‘k’ is the kinetic
constant or reaction rate constant which is independent of concentration and depends on
temperature.

For reactions A+B → C+D

dC
γa =
− a =kC αA C Bβ
dt

Here α is the order with respect to A and β is the order with respect to B

This power law approach can also be used for solid catalytic reactions. This analysis is
simple. The major disadvantage of this method is that it ignores all the factors associated
with adsorption and reaction mechanism on surface of solid catalyst. Hence, power law
kinetics fails to adequately describe any solid catalytic process and the rate equation
derived from mechanistic model is more preferred. Power law kinetics is preferred as a
mode of obtaining preliminary value of rate parameters for solid catalyzed reactions.

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Langmuir-Hinshelwood –Hougen-Watson(LHHW) model

The rate equation derived from mechanistic model that simulates the actual surface
phenomenon during the process is preferred for reactions involving solid catalysts. The
Langmuir-Hinshelwood–Hougen-Watson(LHHW) approach is one of the most
commonly used way of deriving rate expressions for fluid solid catalytic reactions. The
advantages of this method are that :

(1) Rate derived by this method takes into account the adsorption-desorption process
occurring over the surface along with the surface reaction.
(2) Rate equation derived can be extrapolated more accurately to concentrations lying
beyond the experimentally measured values.
During this method of derivation of rate expression, all the physical transport steps like
mass transfer from bulk phase to catalyst surface or diffusion of reactants from pore
mouth to interior pore (intraparticle diffusion) are excluded. Thus, it is assumed that the
external and internal mass transport processes are very rapid relative to the chemical
rate process occurring on or within the catalyst particle. The chemical rate depends on :
(1) chemisorption steps
(2) surface reaction steps
(3) desorption steps

This simple kinetic model assumes isothermal condition about and within catalyst that is
temperature gradient is zero.
In LHHW model development, the rate equation is first derived in terms of surface
concentration of adsorbed species and vacant sites. Then, these surface concentrations are
related to the fluid or bulk concentration that is directly measurable.
For the reaction A + B  C + D

Let ra = rates of adsorption ( g mol/s.gm of


catalyst)

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rs = rates of surface reaction ( g mol/s.gm of catalyst)

rd =rates of desorption ( g mol/s.gm of catalyst)

C AS = concentration of adsorbed A on surface ( g mol/gm of catalyst)

C BS = concentration of adsorbed B on surface (gmol/gm of catalyst)

C cs = concentration of adsorbed C on surface (g mol/gm of catalyst)

C DS = concentration of adsorbed D on surface (g moles/gm of catalyst)

CO = total concentration of active sites on surface (g mol/gm of catalyst)

CV = concentration of vacant sites on surface (g mol/gm of catalyst)

C A = concentration of A in bulk gas phase (g mol/cm3)

Similarly C B , CC , C D are the concentrations of B,C,D in the bulk gas phase,


respectively.

Let the reaction follows the mechanism given below ;

(1) A + S  A.S --- Adsorption of reactant A on surface vacant site S


(2) B + S  B.S --- Adsorption reactant B on surface vacant site S
(3) A.S + B.S  C.S + D.S --- Surface reaction between adsorbed A and B
(4) C.S  C + S --- Desorption of product C from surface creating a vacant
site
(5) D.S  D + S ---Desorption of product D from surface creating a vacant
site

Among the various steps described, the slowest step controls the overall rate of reaction
and the other remaining steps are assumed to be at near equilibrium conditions. This
approach greatly simplifies the overall rate expression, reducing the number of rate
constants and equilibrium constants to be determined from experimental data. Further

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each step in this method is assumed to be elementary and the number of sites is conserved
in each step.

Therefore, the controlling step can be either of the following:

(1) Surface reaction


(2) Adsorption
(3) Desorption

Now total concentration of active sites on surface, CO , will be the summation


concentrations of all sites on which either reactants or products are adsorbed and the
concentration of vacant sites.

∴ CO = CV + C AS + C BS + CCS + C DS

Where, CV is the concentration of vacant sites.

Case 1 : Rate is surface reaction controlling

The surface reaction is the slowest step and is the rate controlling. According to the
mechanism, surface reaction occurs between adsorbed A and adsorbed B producing
adsorbed C & adsorbed D.

AS + BS  CS + DS

The rate of surface reaction is given as

=rS k S C AS C BS − k S' CCS C DS k s = rate constant for forward surface reaction

k S' = rate constant for reverse surface reaction

 k S' 
= k S C AS C BS − CCS C DS 
 kS 

 1  kS
= k S C AS C BS − CCS C DS   KS = (1)
 KS  k S'

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Now, since all the other steps are considered to be in equilibrium, therefore concentration
of adsorbed species can be obtained as follows.

For adsorption steps and desorption steps :

C AS CCS
From step (1) KA = From step (4) K C =
C A.CV CC .CV

C BS C DS
From step (2) KB = From step (5) K D =
C B .CV C D .CV

K A , K B , K C , K D are adsorption equilibrium constants.

Then, the adsorbed phase concentrations can be written as

C AS = K AC ACV CCS = K C CC CV

C BS = K B C B CV C DS = K D C D CV

Substituting all these value in equation (1)

 1   K 
rS =k S C AS C BS − CCS C DS  =k S  K AC ACV . K B C B CV − C CC CV . K D C D CV 
 KS   KS 

 K K 
=or, rs k S  K A K B C AC B CV2 − C D CC C D CV2 
 KS 

 KC K D 
=or rS k S K A K B C AC B − CC C D  CV2 (2)
 KS K AKB 

Now , CO = C AS + C BS + CCS + C DS + CV

CO = K AC ACV + K B C B CV + K C CC CV + K D C D CV + CV

=CV [1 + K AC A + K B C B + K C CC + K D C D ]

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CO
CV = (3)
1 + K AC A + K B C B + K C C C + K D C D

For the reaction A+B  C+D , at equilibrium , the overall equilibrium constant is
CC C D
K= .
C AC B

All concentrations correspond to the equilibrium conditions in gas phase.

( C / K C CV )( C DS / K DCV )
K = CS =
CCS C DS K A K B CV2
.
( C AS / K ACV )( C BS / K BCV ) C AS C BS K C K D CV2

KAKB CCS C DS
Or , K = .K  KS = (4)
KC K D S C AS C BS

Substituting (3) &(4) in equation (2),

 1  CO2
=rS k S K A K B  C AC B − CC C D 
  ( 1 + K AC A + K B C B + K C C C + K D C D )
2
K

1
C AC B − CC C D
rS = k S K A K B C
2 K (5)
( 1 + K AC A + K B C B + K C C C + K D C D )
O 2

The above rate expression can also be derived in terms of bulk partial pressure.

Case 2: Rate is adsorption control

(a) Adsorption of A controlling

Let adsorption of A be the slowest step so that adsorption of B, surface reaction and
desorption of C are at equilibrium.

Adsorption of A is given as

A + S  AS

=
Rate of adsorption ra ka C ACV − kd C AS

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 k 
=ra ka C ACV − d C AS 
 ka 

 1  ka
=
Or, ra ka C ACV − C AS  KA = (adsorption equilibrium constant for A)
 KA  kd

 1 C AS 
=ra ka CV C A −  (6)
 K A CV 

Now as other steps are in equilibrium :

CCS C DS
KS =
C AS C BS

C BS C C
KB = K C = CS K D = DS
C B CV CC CV C D CV

C BS = K B C B CV CCS = K C CC CV C DS = K D C D CV

Then ,

CCS C DS K C CC CV . K D C D CV K C K D CC C D CV
C AS = = =
K S C BS K S K B C B CV KS KB CB

Substituting value in equation (6)

 1 K C K D CC C D CV 
=ra ka CV C A − 
 K ACV K S K B CB 

 K C K D CC C D 
=ra ka CV C A − 
 K S K A K B CB 

 1 CC C D 
=ra ka CV C A −  (7)
 K CB 

KS KAKB
K= = Overall equilibrium constant.
KC K D

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Now C 0 =CV + C AS + C BS + CCS + C DS

K C K D CC C D CV
=
CV + . + K B C B CV + K C CC CV + K D C D CV
KS KB CB

 K K K C C  
=CV 1 + C D A  C D  + K B C B + K C CC + K D C D 
 K S K A K B  CB  

 K C C 
=CV 1 + A C D + K B C B + K C CC + K D C D 
 K CB 

CO KS KAKB
CV = K =
K A CC C D KC K D
1+ + K B C B + K C CC + K D C D
K CB

Substituting value of CV in equation (7)

C C 
CA −  C D 
ra = ka C 0  KC B  (8)
K C C
1 + A C D + K B C B + K C CC + K D C D
KC B

For a given catalyst C 0 is constant.

Similarly expression when desorption of product is the rate controlling step can be
derived. For desorption of C controlling the whole reaction, the rate expression can be
derived as

C C 
C AC B −  C D 
rd = kd C 0 K  K 
1 + K AC A + K B C B + K C KC AC B + K D C D

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Eley Rideal model

Apart from power law and Langmuir-Hinshelwood models, other kinetic models are also
used to fit the data. EleyRideal model depicts the reaction mechanism in which one
reactant species (say A) is adsorbed while the second reactant species (say B) is not
adsorbed on the catalyst surface. The reaction then occurs when the passing gas
molecules of B in gas phase directly reacts with the adsorbed species A. The schematic
representation is shown in Fig. 1.

Fig. 1. Eley Rideal mechanism for reaction of adsorbed A with gas phase B producing product AB

(1) A + S  AS
(2) AS + B (g) → P

Assuming that step 2, the reaction between adsorbed A and gas phase B is irreversible
and the rate determining step, then the rate of reaction can be written as

r = k CAs CB (9)

The concentration of adsorbed A can be given as CAS = K A CA CV

Now , CO = CAS + CV = K A CA CV + CV = CV (1 + K A CA )

CO
CV =
1 + K A CA

K A C A CO
CAS =
1 + K A CA

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Substituting value of CAS in equation (9)

kCO K A CA CB
=r k=
CAS CB
1 + K A CA

If the products are chemisorbed then the reaction may become reversible as shown below.


AS + B(g) 
k

 PS
k b

PS → P + S

Then the rate expression can be written as

=r k CAs CB − k b CPs

The concentration of adsorbed product is CPS = K P CP CV

CO = CAS + CPs + CV = K A CA CV + K p CP CV + CV = CV (1 + K A CA + K P CP )

CO
CV =
1 + K A CA + K P CP

K A C A CO
=CAS K=
A CA CV
1 + K A CA + K P CP

K P C P CO
=CPS K=
P CP CV
1 + K A CA + K P CP

Substituting CAS and CPS in rate expression,

 1  k
=
r k CAs CB − k b C=
Ps k  CASCB − CPS  =
K
 K  kb

 K A C A CO 1 K P C P CO 
r k  CB − 
 (1 + K A CA + K P CP ) K (1 + K A CA + K P CP ) 

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 KP 
 K A CA CB − CP 
r = kCO  
K
1 + K A CA + K P CP

Estimation of model parameters

The various parameters in the kinetic models such as rate constants, reaction orders, and
equilibrium constants are derived by fitting the experimental data. The optimal values of
the parameters in the rate equation of a heterogeneous reaction are determined
traditionally by using gradient or direct search methods. For success of this method, a
very good initial estimate of the parameters is required. This proves to be difficult in most
cases. If the initial estimates are far from the global optima, then it is likely that the
gradient or direct search method will not converge at all or will converge to local optima.
Recently genetic algorithm (GA) is increasingly applied in estimation of kinetic
parameters. The major advantage of this method is that it is not dependent on the initial
estimate of the parameters. GA performs a multi-directional search.

Book Reference

• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981


• J.J. Carberry, Chemical and catalytic reaction Engineering, Dover Publications, 2001
• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India,1999
• R. J. Farrauto and C. H. Bartholomew, Fundamentals of Industrial catalytic
Processes, Blackie Academic & Professional, 1997

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Lecture 20

Analyzing data from laboratory reactors

The objectives of analyzing data include


• Determining catalyst activity, selectivity and stability
• Determining the effect of important process variables such as temperature,
pressure, reactant concentrations
• Finding a rate equation

Elimination of mass transfer and pore diffusion limitations

In a solid catalyzed reaction, the presence of mass transfer and pore diffusional
resistances can significantly affect the rate of the reaction. The details will be discussed
in lecture no. 22 to 24. To ensure that no internal or external mass transfer resistances are
present under the operating conditions, preliminary experiments are carried out.

Elimination of mass transfer limitations

For checking if external mass transfer is affecting the rate of reaction, conversion data is
obtained by increasing the flow rate of the feed but keeping the W/FAO constant. Fig. 5
shows the plot of conversion as a function of linear velocity of fluid at constant W/FAO at
a given temperature, usually the highest temperature is used during reaction.

Fig. 5. Typical plot of conversion as a function of linear velocity of fluid at constant W/FAO and temperature

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It can be observed that at low fluid velocity, conversion increases with increasing fluid
velocity and subsequently becomes constant at higher flow rates, implying that external
mass transfer does not affect the rate of reaction at this fluid velocity. Due to external
mass transfer limitation the concentration of reactant near catalyst surface is lower than
the bulk phase concentration. The effect is maximum at lower fluid velocity when the
resistance to transport is considerable. With increase in fluid velocity, the turbulence
effectively enhances the mixing in fluid phase and the concentration of reactant near the
catalyst surface approaches the bulk phase concentration. Consequently reaction rate
increases increasing the conversion. At high velocity due to high turbulence the mass
transfer limitation is totally removed and the reactant concentration near the catalyst
surface becomes equal to that of bulk phase concentration and the conversion reaches the
maximum limiting values. Thereafter any change in fluid velocity does not affect the
conversion as shown in the figure. Kinetic study should always be carried out at
conditions where the effect of external mass transfer on conversion is negligible.

Elimination of pore diffusion limitations

rp ρp
Weisz criterion Rs2 ≤ 1 can be used to determine the significance of intraparticle
Cs De
diffusion. Here Rs=pellet radius; rp=observed rate; ρp = pellet density, Cs = surface
concentration; De effective diffusivity. Reactions should be carried out at the conditions
when Weisz criterion is satisfied so that the intraparticle diffusion could be neglected for
these operating conditions. This is discussed in details in lecture no. 24. The effectiveness
of porous catalyst can also be determined experimentally by measuring conversion with
successively smaller catalyst pellets until no further change in conversion occurs. The
pore diffusion resistance decreases the concentration within the pellets thereby decreasing
the conversion. The pore diffusion resistance is considered to be negligible for the
catalyst size range for which the conversion does not change with size. For study of
intrinsic reaction kinetics, catalyst pellet size is chosen where the intraparticle diffusion
could be neglected.

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Elimination of homogeneous phase reaction and deactivation

When reaction is carried out over a fixed bed of solid catalyst there may be possibility of
non-catalytic homogeneous reactions occurring in gas phase. If any non-catalytic
homogeneous reactions occur along with heterogeneous catalytic reactions, then data
collected will give erroneous kinetics for the heterogeneous reaction. Hence, reaction
should be carried out in an empty reactor without using any catalyst to determine the
contribution of homogeneous phase reactions, if any, at the desired operating conditions.
Kinetic study should be carried out at operating conditions for which contribution of
homogeneous phase reactions is negligible.
In addition, deactivation studies should be carried out by operating the reactor for long
run lengths. If any significant deactivation occurs, than it should be taken into account for
further analysis.

Integral analysis of rate data


In this method a series of run are made in a packed bed at a fixed initial concentrations
CA0 and a fixed temperature while varying the catalyst mass W and/or initial molar flow
rate FA0 to generate a range of W/FA0 values at different conversions XA. A rate equation
is then selected for testing using the design equation for packed bed reactor.
x Af
W dX A
FAo
= ∫
0
−rA (1)

First simpler rate equations such as zero order, first order, second order irreversible are
tried. Mechanistic reaction models can also be tested. The W/FA0 and the right hand
integral in equation (1) are evaluated numerically and plotted to test for linearity (Fig 1).
Linearity of the plot is used as criterion for judging if the selected rate equation is a
useful model for the data i.e consistent with the data. If not then another rate equation
may be tried.

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W/FA0

x Af
dX A
∫0
− rA

Fig. 1. Typical plot of W/FA0vs integral value for linearity test in integral analysis of rate data

Differential analysis of rate data


In this method, the data are collected as in the previous case. A plot of conversions XA
versus W/FAo is made for each set of runs at a fixed temperature (Fig 2) . A best fit of
data is made.Tangent to the fitted curve are drawn at regular interval along the curve
corresponding to the best fit. The slopes of this tangent are evaluated which correspond to
dX A
the reaction rate −rA =
d(W / FAo )

T constant
XA

Tangent slope=-rA

W/FA0
Fig. 2. Typical plot of XA vs W/FA0 for determination of rate from tangent slope in differential analysis of data

Tangents can be evaluated more accurately by differentiating the equation for best fit of
data and evaluating the derivative at various intervals over the data set. Values of –rA
versus CA are plotted to determine the reaction orders. For example for an irreversible
reactions in which data are fitted by a simple power rate law − rA =
kC An , a plot of ln(-rA)

vs lnCA is linear with a slope of order n. The rate constant value can be determined from

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the intercept. If rate vs temperature data available then it is possible to determine the
apparent activation energy from Arrhenius equation k = A exp(-E/RT). The slope of the
plot of ln k vs 1/T gives the activation energy E of the reaction.

ln k Slope = E

1/T

Fig. 3. A typical Arrhenius plot for determination of activation energies

Linear and nonlinear regression of rate data


k p A pB
For a Langmuir –Hinshelwood type rate equation −rA = , the value
1 + K Ap A + K BpB
of rate law parameters k, KA, KB cannot be analyzed as simply as in power law kinetics.
The rate law parameters can be determined by linear least square or nonlinear least square
method. In linear least square method, the above LH rate equation can be linearized by
dividing throughout by pA and pB and inverting it as shown below:

p ApB 1 K A K
− =+ p A + B pB
rA k k k
The parameters can be estimated by multiple regression technique using the following
equation for N experimental runs. For the ith run :

Yi =
ao + a1 X1i + a 2 X 2i

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The best values of the parameters a0, a1 and a2 are found by solving following three
equations

N N N
∑ Yi =
Nao + a1 ∑ X1i + a 2 ∑ X 2i
=i 1 =i 1 =i 1
N N N N
∑ ∑
X1i Yi = ao X1i + a1 X1i
2
∑ ∑
+ a 2 X1i X 2i
=i 1 =i 1 =i 1 =i 1
N N N N

X 2i Yi = ∑ ∑
ao X 2i + a1 X1i X 2i + a 2 X 2i
2

=i 1 =i 1 =i 1 =i 1

The above LH rate equation can also be solved by non-linear regression analysis. Usually
linearized least square analysis is used to obtain the initial estimates of the rate
parameters and used in non-linear regression. In non linear analysis the rate law
parameters are first estimated to calculate the rate of reaction ‘rc’. Then the values of rate
law parameters that will minimize the sum of the squares of difference of the measured
reaction rate rm and the calculated reaction rate rc , that is the sum of (rm-rc)2 for all data
points, are searched. If there are N experiments with K number of parameter values to be

determined then the function to be minimized is given by σ =∑ 2


N
( rim − ric ) 2
i =1 N−K
Here rim and ric are the measured and calculated reaction rate for ‘i’th run respectively.

The parameter values giving the minimum of the sum of squares, σ 2 , can be searched by
various optimization techniques using software packages.
Initial rate analysis
Initial rate analysis for a reaction may be done to understand the mechanism of a reaction.
Initial rate is defined as the rate at zero conversion. It is obtained by extrapolation of the
rate vs conversion data to zero conversion. For higher accuracy, the conversion data are
collected at very low conversion region. In this method, the dependence of initial rate
data on partial pressure or total pressure of the reactant is studied.

Consider the reaction A+B C+D

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The rate expression derived from Langmuir Hinshelwood model when surface reaction is
controlling is

1
CA CB − CC C D
rS = k S K A K BCO2 K (2)
(1 + K A CA + K BCB + K CCC + K D CD )
2

Now at zero conversion all the product concentration will tend to zero, hence putting CC
=0 & CD =0, the rate expression [2] simplifies to

CA CB
ri = k S K A K BCO2 (3)
(1 + K A CA + K BCB )
2

whereri is the initial rate. Now, if a equimolal initial concentration of CA and CB is used
pA
then CA=CB . Then assuming ideal gas mixture, CA = , where p A is the partial
RT
pressure of A.

pB
Similarly CB = where p B is the partial pressure of B .
RT

pt
Now since it is an equimolal mixture, then at initial condition. p=
A p=
B where pt is
2
the total pressure.

pt
Or C=
A C=
B
2RT

Then substituting CA and CB in equation [3] becomes

2
 pt 
 
ri = k S K A K BCO2  2RT 
2
 pt pt 
1 + K A + KB 
 2RT 2RT 

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 k K K C2 
p 2t  S A 2 B2 O 
Or ri =  4R T 
2
  KA + KB  
1 +  2RT  p t 
   

Ap 2t
ri =
Or
[1 + Bp t ] 2

k S K A K BCO2 K + KB
Where A = 2 2 and B = A
4R T 2RT

On plotting initial rate ri as a function of total pressure pt , a typical curve as shown in


Fig 4A is obtained. Hence if kinetic data for a reaction give similar plot then it can be
deduced that the reaction is surface reaction controlled.

When adsorption of A is controlling the dependence of initial rate on total pressure can

Ap t
be derived in similar way as ri =
1 + Bp t

k a CO K
Where A = and B = B
2RT 2RT

For this mechanism a typical plot of initial rate ri as a function of total pressure pt is
shown in Fig 4B. When reaction data satisfy this plot then the reaction is said to be
adsorption A controlling. In similar way other models can be tested for fitting.

However, it should be noted that though the initial rate analysis is simple and can reduce
the number of rate expressions to be tested against the experimental but cannot substitute
a differential or integral analysis. It should be used as only as preliminary kinetic analysis
method.

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A B

ri ri

Pt Pt

Fig. 4.Typical plot for initial rate vs total pressure for reactions A + B  C + D when equimolal mixture of A and B is
used.A ) surface reaction controlling B) adsorption of A controlling

Book Reference

• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981


• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India.,
1999
• R. J. Farrauto& C. H. Bartholomew, Fundamentals of Industrial catalytic Processes,
Blackie Academic & Professional, 1997
• O. Levenspiel , Chemical reaction engineering, John Wiley & sons. 1995
• J.J. Carberry ,Chemical and catalytic reaction Engineering, Dover Publications, 2001.

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Lecture 21

Solved example

1. A catalytic reaction, A → 4B is studied in a packed bed reactor using various


amount of catalysts. The out let concentration and corresponding conversion is given
in following Table 1. Given FA0 = 2 mol / h and CA0 = 0.1 mol / litre

The rate equations for this reaction can be calculated using


i. Integral method of analysis
ii. Differential method of analysis

Table 1:

Runs 1 2 3 4 5

Catalysts used, kg 0.02 0.04 0.08 0.12 0.16

CA,out, mol/litre 0.075 0.061 0.045 0.035 0.028

XA 0.07 0.15 0.25 0.33 0.36

(i) For integral analysis


The design equations for packed bed reactor is given as

x Af
W dX A
FAo
= ∫
0
−rA

Assuming a first order kinetics −rA =


kCA and substituting
x Af
W dX A
Then
FAo
= ∫
0
kCA

CAO (1 − X A ) 4 −1
Now CA = Where ε= = 3
1 + εA X A
A
1

ɛA is the fractional change in volume of the system between no conversion and complete
conversion of reactant A.

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1 + εA X A
x Af x Af
W dX A 1
Or=
FAo ∫0=
kCA kCAO ∫ (1 − X ) dX
0 A
A

For first order irreversible reaction for plug flow, integrated from of RHS for any
constant of ε A is as follows.

W 1
Or kCAO= (1 + εA ) ln −ε X (1)
FAO (1 − X A ) A A

Substituting values of C AO , FAO , ε A in equation (1)

W 1
=
  k 4 ln − 3X A
 20  (1 − X A )

 W    1 
Hence plotting   k  vs  4 ln − 3X A  a straight line is obtained.
 20    (1 − X A ) 

It suggests that assumption of first order kinetics is correct. The rate constant can be
obtained from slope of the plot which is 95.8 litres/hr.kg catalyst

The rate equation can be written as −rA =


kCA =[95.8 litres/hr.kg catalysts] C A

0.8 y = 95.8x
1 0.6
4 ln − 3X A
( XA )
1 − 0.4

0.2

0
0 0.002 0.004 0.006 0.008 0.01

W
 k
 20 

W   1 
Fig. 6. Plot of  k  4 ln − 3X A 
(1 − X A )
vs in integral analysis of data
 20   

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(ii) For differential analysis

dX A
−rA =
d(W / FAo )

W W/FAo XA - rA (Calculated from


slope Fig 7A)

0.02 0.01 0.07 7.2

0.04 0.02 0.15 6.1

0.08 0.04 0.25 4.3

0.12 0.06 0.33 3.1

0.16 0.08 0.36 2.3

The XA vs W/FAO plot is shown in Fig 7(A) and used to calculate rate.

0.45
8
0.4
0.35
A BB y = 95.6x
6
0.3
-rA

0.25 4
XA

0.2
0.15 2
0.1
0.05 0
0
0 0.02 0.04 0.06 0.08 0.1
0 0.02 0.04 0.06 0.08
W/FAO CA

Fig. 7. Plots for differential analysis of data (A) XA vs W/FAO (B) rA vs CA plot

If − rA is plotted against CA a straight line is obtained of slope k (Fig 7B). Since the line
is straight line passing through origin, the order of the reaction is one as also obtained
from integral analysis.

Hence the rate is −rA =


kCA =[95.6 litres/hr.kg catalysts] C A

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Book Reference

• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981


• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India.,
1999
• O. Levenspiel , Chemical reaction engineering, John Wiley & sons. 1995

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Lecture 22

Effect of transport processes

Effect of external transport on catalytic reaction rate

Transfer of reactants from bulk fluid to surface of catalyst particles depends on the
concentration difference which is affected by the velocity pattern of fluid near the
catalyst surface, physical properties of fluid and intrinsic rate of chemical reactions.
While the fluid properties affect the mass transfer between fluid and catalyst surface, the
intrinsic rate is determined by the condition and properties of catalyst. The external
concentration profiles for reactant for solid catalytic reaction in absence and presence of
mass transfer limitation is shown in Fig. 1. In absence of mass transfer there is no
difference in concentration of reactant at bulk and near the catalyst surface. However,
presence of significant mass transfer resistance results in a decrease in the concentration
of reactants at the catalyst surface compared to that in the bulk fluid. Consequently, the
observed rate is less than the intrinsic rate evaluated at bulk fluid reactant concentration.

In addition to mass transfer limitation, there may be a temperature difference between the
bulk fluid and catalyst surface. The magnitude depends on the heat transfer coefficient
between the fluid and catalytic surface, reaction rate constant and heat of reaction. If the
reaction is endothermic, the temperature at the catalyst surface will be less than the bulk
fluid temperature and the observed rate will be less than that determined at the bulk fluid
temperature. If the reaction is exothermic, the temperature of catalyst surface will be
more than the bulk fluid temperature. Therefore, the observed rate will be higher or lower
than corresponding bulk fluid conditions, depending on both heat transfer and mass
transfer effects. Rate at the surface will be higher due to heat transfer limitations and
lower due to mass transfer limitations. Depending on the relative magnitude, the overall
rate will be increased or decreased. Discussion in subsequent sections is limited to
isothermal conditions.

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CBulk With mass transfer limitations CSurface < CBulk

CSurface

CBulk Without mass transfer limitations CSurface = CBulk


CSurface

Fig. 1. External concentration profiles for reactant for solid catalytic reactions in absence and presence of mass transfer
limitations

Reaction rate in presence of significant external mass transfer limitation

Consider a gaseous irreversible reaction A  B that is occurring on a solid catalyst.


Assume the reaction to be of first order with respect to A. Since the reaction is
irreversible, the concentration of B at the catalyst surface does not influence the rate.
Also assume desorption of B to be very fast (path -3).

Hence the reaction is controlled by the following two steps

1. transportation of A from bulk to catalyst surface (path -1)


2. reaction of A to B at catalyst surface (path -2)

A B
rd
Path-1

A rS
→B
Path-2
Path-3

=
Diffusion rate of A from bulk gas to surface is rd km am ( C b − C s ) (1)

Surface reaction rate is rs = kC s (2)

Here, rate is mol /s. g catalyst.

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Where,

Cb = bulk gas concentration of A, mol/cm3


Cs = catalyst surface concentration of A, mol/cm3
k m = mass transfer coefficient between bulk gas and solid surface , cm/s
a m = external surface area, cm 2 /g
k = reaction rate constant, cm3 /s.g catalyst for first order recation

At steady state, rate of diffusion and surface reaction rate will be equal. Hence rd = rs

And overall reaction rate can be expressed by either of two

rd= r=
s rp (3)

Here, rp is the steady state rate per unit mass of catalyst pellets.

From (1) , (2) and (3)

rp k m a m ( C b − =
Or,= C s ) kC s (4)

km am
Or , C s = C
k + km am b

Substituting the value of Cs in rp = kC s

k km am
= =
rp kC C (5)
s
k + km am b

Or rp = koC b

k km am
Where ko = . The ko is called the overall rate constant.
k + km am

Equation (5) is the rate expression at steady state for a first order reaction in terms of bulk
concentration when significant mass transfer limitation is present.

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k km am
Now , ko =
k + km am

1 1 1
Or. = +
ko k k m am

Case 1 : When diffusion controls the process, that is reaction is very fast then
k >> km am . Hence from equation (5) it can be written as

k km am k km am
=rp = Cb Cb
k + km am k

Or rp = km am C b (6)

Case 2 : When surface reaction controls the overall process ,that is diffusion is very fast
then k << km am

Hence from equation (5) it can be written as

k km am k km am
=rp = Cb C
k + km am km am b

Or rp = k C b . (7)

Mass transfer coefficient in packed bed for solid-fluid system

Average transport coefficient between bulk stream and particle surface can be determined
from following correlation in terms of dimension less groups characterizing the flow
conditions.

23
K ρ  a  m 
jD = m  m   
G  at   ρD 

Where am is the effective mass transfer area and at is the total external area of the
particles. For Reynolds number greater than 10, the following relationship can be used.

−0.407
0.458  dG 
j=  
εB  m 

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Where,

G = superficial mass velocity based upon cross sectional area of empty reactor = uρ

dp = diameter of spherical catalyst particles

µ = viscosity of fluid

ρ = density of fluid

D= molecular diffusivity of component being transferred

εB = void fraction of the bed

Other correlations are also available in the literature.

Effect of external mass transfer resistance on order of reaction

Consider a irreversible and gas phase reaction A → B . Assume true order of the
reaction to be n = 2 . Hence actual reaction rate can be written as,

rp = k C s2

Now if the rate is mass transfer controlled, then from (6) rate is given as rp = km amCb

Experimental data plotted as rate vs Cb will give a straight line (passing through origin).

Now if the external diffusion is not taken into account then based on the experimental
data it will be assumed that reaction is first order with respect to concentration because
for first order reaction, rp = kCb , the plot of rate versus concentration gives a straight line

with slope k passing through the origin. Hence in this case, the rate will be interpreted as
rp = kCb and the order will be interpreted as one. However, this interpretation will be a

false conclusion as actual order of the reaction is two and it is appearing one only because
external diffusion is controlling the process. Regardless of the intrinsic kinetics, if
external mass transfer is controlling, the experimentally determined order will always
appear as unity.

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Effect of external mass transfer resistance on activation energy of reaction

Consider an irreversible and gas phase reaction A → B . Assume the reaction to be first
order with respect to A.

Then, rp = k0C b where k0 = overall rate constant

Rates are measured over a nonporous catalyst at different temperature and observed rates
are used to calculate the overall rate constant k0 . The corresponding activation energy
can be obtained from Arrhenius equation as follows

− E'
k0 = A e' RT

Here the activation energy E ' is known as apparent activation energy and A' as apparent
frequency factor. This E ' is not the true activation energy corresponding to surface
reaction as we will see in the following section.

Now k0 overall rate constant is given as

k km am
Or , k0 = (8)
k + km am

−E
If E is the true activation energy of the surface reaction then by substituting k = Ae RT in
equation (8)

−E
Ae RT km am
k0 = −E
Ae RT
+ km am (9)
−E
1. At high temperature , Ae RT >> km am
Then from equation (9) , k0 ≅ km am which is nearly a constant value as km is
relatively insensitive to temperature

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−E −E
(2) At low temperature, Ae RT
<< km am , then k0 ≅ Ae RT
and a straight line is
obtained on Arrhenius plot.

If the Arrhenius equation is plotted over the entire range of temperature, then at low
temperatures, the slope corresponds to the correct (or true) activation energy E of the
surface reaction. As temperature increases, a curve is obtained, which flattens to a
horizontal line corresponding to constant value of ‘ km am ’. Hence when experimental rate
data for fluid solid catalytic reaction shows a curved Arrhenius plot then it is possible that
mass transfer resistance is significant and external diffusion plays an important role in
kinetics. This situation is for isothermal conditions.

Fig. 2. Arrhenius plot for reaction (a) without external mass transfer resistance

and (b) with external mass transfer resistance

Effect of external transport on selectivity

For multiple reactions, obtaining high selectivity of the desired products is important.
The effect of external transport on selectivity depends on the kinetics of the system.
Selectivity at any location in a reactor can be defined as the ratio of the rates of the
desirable to the undesirable product. The effect will be discussed at isothermal conditions
only.

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Case 1 : Isothermal-consecutive reaction:

Consider a first order irreversible consecutive reaction

A 
k1
→ B 
k2
→C

rB k1C AS − k2CBS
The selectivity of B w.r.t C, S B can be written as S=
B = (10)
rC k2CBS

The surface concentration can be expressed in term of bulk values.

For A,

(km am ) A ( C A − C As ) =
k1C As

(km am ) A C A
Or, C As =
k1 + ( km am ) A

Similarly for B, (here B is diffused from surface to bulk)

( km am ) B ( CBS − CB ) = k1C AS − k2CBS

k1C AS + ( km am ) B CB
Or, CBS =
( km am ) B + k2

Here CA and CB are bulk concentrations of A and B, respectively

Substituting value of CAS

(k )
k1 k1 +m( kmm aAm )A + ( km am ) B CB
a C

CBS = A

(km am ) B + k2

Substituting value of C AS & CBS in S B (10), selectivity can be obtained in term of bulk
concentration

k1C A  1 + k2 / (km am ) B 
SB   −1 (11)
k2CB  [ k1 / (km am ) B ] (C A / CB ) +  ( k a1 )  [ (km am ) A + k1 ] 
  m m A 

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In absence of mass transfer resistances Cs = Cb for both A & B

Then, the above equation reduces to

rB k1C A − k2Cb
S=
B =
rC k2CB

k1C A
=
SB −1 (12)
k2CB

The term in brackets of equation (11) is less than unity hence comparison of (11) & (12)
suggests that selectivity is reduced by mass transport effect. As a mass transfer resistance
becomes insignificant, the term in bracket in (11) approaches unity and it is in agreement
with equation (12).

Qualitatively, the effect of external mass transfer can be explained as follows. The mass
transfer limitation will reduce the surface concentration of A below the bulk value. This
will reduce rate of formation of B by the first reaction. Again, due to mass transfer
resistances in removal of B from the surface, concentration of B will increase near the
catalyst surface and thereby result in an increase in the rate of disappearance of B to C by
the second reaction. Thus, qualitatively it can be seen that formation of B is reduced
while disappearance of B is increased due to external mass transfer effect. Consequently,
selectivity of B with respect to C is reduced by external mass transfer limitations.

Case 2 : Parallel reaction (isothermal)

Consider two parallel first-order reactions from the same reactant with B as the desired
product.

A 
k1
→ B Desired product

A 
k2
→C

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The selectivity of B w.r.t C is given by :

rB k1C AS k1
S=
b = =
rC k2C AS k2

Hence selectively is independent of concentration. Hence, external mass transfer does not
affect the selectivity in this case. For this type of parallel reaction, the rate is reduced
by mass transfer but the selectivity is unchanged.

If the parallel reactions are completely independent

A 
k1
→B

R 
k2
→S

Selectivity is then given as

 1 1
+
rB k1C AS  ( km am ) R k2  C A
S= = =  
rS k2CRS  1 1  CR
B
+
 ( km am ) k1 
 A

k1 C A
In absence of external resistance, selectivity is S B' =
k2 CR

Effect of external mass transport on selectivity is given by ratio

S B  ( km am ) R + k2  ( km am ) A
= 
S B'  ( km am ) A + k1  ( km am ) R

The two mass transfer coefficients are nearly the same for most reaction systems. Hence
the ratio becomes

S B ( km am ) R + k2
=
S B' ( km am ) A + k1

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The selectivity in this case will decrease by external mass transfer only if k1 > k2

For low mass transfer resistance , no effect on selectivity will be observed as


S
km am >> k2 or k1 then B' = 1
SB

Book Reference :

• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981


• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India., 1999
• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications, 2001
• O. Levenspiel , Chemical reaction engineering, John Wiley & sons, 1995

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Lecture 23

Effect of internal mass transport on catalytic reaction rate

Diffusion

Diffusion of reactants within pores is a complex phenomena and results from the
contribution of :

1. Bulk diffusion : Diffusion due to concentration or pressure gradients. The molecules


collide with each other.
2. Knudsen diffusion : Diffusion in fine pores governed by molecular velocity and as
well as diameter of pore. The diffusing molecule is more likely to collide with a wall
rather than another molecule. It is important at low pressures and for pore size below
50 nm.
3. Surface diffusion: Transport of adsorbed molecules on a surface by hopping
mechanism that is adsorbed molecules tend to migrate to an adjacent empty site if it
has sufficient energies to jump or overcome the energy barrier. However, in most
cases contribution of surface diffusion to total transport is very small and generally
neglected.
For macroporous material with large pore size such as alumina pellets of mean radius of
8000 A0 , bulk diffusion would prevail in these pores at atmospheric pressure. As the size
of the pore decreases, diffusion in the pores is more and more influenced by pore walls
and transport is dominated by Knudsen mechanism. Hence in micropores, particularly
for gaseous system, transport can be assumed to be entirely by Knudsen diffusion.

The pressure also affects the relative contribution of bulk and Knudsen diffusion for
gaseous system. The mean free path is inversely proportional to pressure. Increase in
pressure decreases mean free path and probability of collision between molecules
increases. Consequently, bulk diffusivity becomes more important as the pressure is
increased. On the other hand, as pressure is lowered mean free path is reduced and
probability of molecules colliding with the walls is increased. Consequently, transport is
dominated by Knudsen diffusion.

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The diffusion in binary system is represented by Fick’s law which states that molar flux
of a species relative to an observer moving with molar average velocity is proportional to
the concentration gradient of the species. If A diffuses in a binary mixture of A and B ,
dCA
then according to Fick’s law the flux of A is expressed as J A = − DAB
dz

Here DAB is the proportionality constant called the diffusion coefficient or diffusivity of
A in mixture of A and B.

Different binary diffusion conditions may exists :

1. Equimolar counter diffusion, NB= - NA


2. Non-equimolar counter diffusion, NB ≠ - NA
3. Diffusion of A through non diffusing B, NB= 0
Here NA , and NB are the molar flux of A and B respectively. The negative sign
correspond to opposite direction.

Assume that for a gaseous irreversible reaction A → B, the reaction and diffusion in a
single cylindrical pore results in equimolal counter diffusion, or NB= - NA . Then for
reactant A, the combined diffusivity in a cylindrical pore is given as

1
D= (1)
1 − α yA 1
+
DAB ( Dk ) A

where DAB is the bulk diffusion contribution and ( Dk ) A is the Knudsen diffusion

contribution.

NB
Here α = 1 + =0 as NB= - NA
NA

1
Or D = (2)
1 1
+
DAB ( Dk ) A

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When pore radius is large ( Dk ) A → ∞ , D = DAB = bulk diffusion. If pore radius is very

small, Knudsen diffusivity is controlling and D = Dk

Bulk diffusivity at moderate temperature and pressure can be evaluated using Chapman –
Enskog equation. For binary gas mixture of A and B

1/ 2
 1 1 
M + M 
3/ 2
T
DAB = 0.0018583  A B 
(3)
ptσ AB Ω AB
2

DAB ( cm 2 / s ) = bulk diffusivity


T ( K ) = temperature
M A & M B = molecular weight of A and B, respectively
pt ( atm ) = total pressure of the gas mixture
σ AB ( A0 ) = constant in Lennard-Jones potential-energy functions for the molecular pair AB
ε AB = constant in Lennard-Jones potential-energy functions for the molecular pair AB
Ω AB =
collision integral

Knudsen diffusivity can be evaluated by the following equation :

1/ 2
 T 
( Dk )=
A
9.7 × 10 a  3
 (4)
 MA 

( Dk ) A → Knudsen diffusivity cm 2 / s
T → temperature , K
a → pore radius, cm

The diffusivity of A in multicomponent system containing n components is given as

n
N A − y A ∑ Ni
i= A
DA,m = n
1
∑ D ( y i N A − y A Ni )
i= A Ai

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Here Ni is taken as positive if diffusion is in same direction as that of A and negative if in


opposite direction. The DAi are the binary diffusivities of component A with respect to
component ‘i’. The yA is molfraction of A and yi molfraction of ‘i’

Effective diffusivity, De

The actual pore network within a catalysts pellet can be quite complex and hence to
account for diffusion through the tortuous, random and interconnected arrangement of
pores it is essential to develop a pore model that can realistically represent the geometry
of void space. The void geometry should also be represented in terms of easily
measurable physical properties of catalyst pellets, such as surface area, pore volume,
density of solid phase and distribution of void volume according to pore size. Keeping all
these factors in consideration, various pore models are developed. The effective
diffusivity (De) is derived using these pore models from combined diffusivity for a single
cylindrical pore.

The steps involved are as follows :

1. Initially combined diffusivity D for a single cylindrical pores is calculated using


1 1
the equation (2) =
D 1 1
+
DAB ( DK ) A

2. Then a geometric model of the pore system is used to convert D to De for the
porous pellet.
Two pore models more commonly used are :

1. parallel pore model


2. random pore model

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Parallel pore model

In this model, the effective diffusivity is derived based on assembly of parallel cylindrical
pores of uniform radius. The interconnection and non-cylindrical pore shapes for real
material is accounted for by introduction of a tortuosity factor δ. Using this model, the
effective diffusivity De can be expressed as

εD
De = (5)
δ

where ε = porosity; D = combined diffusivity ; δ = tortuosity factor

The typical porosity values lies in the range of 0.3- 0.5. The tortuosity factor can varies
from less than one to 6. Typically a value of 3 to 4 is used.

Random pore model

This model considers that pellets consist of both macro and micro pores. Pellets consist
of assembly of small particles containing micropores and the void space between the
particles constitutes the macropores. Transport in the pellet is assumed to occur by
combination of diffusion through the macro-regions having void fraction εM and the
micro regions having void fraction εμ. The magnitude of individual contribution is
dependent on their effective cross-sectional areas perpendicular to the direction of
diffusion.

The resultant expression for effective diffusivity De is given as

ε m2 ( 1 + 3ε M )
De D M ε +
= 2
Dm (6)
1−εM
M

D M and D m are combined diffusivity in macropores and micropores, respectively


and obtained by applying equation for combined diffusivity D to macro and micro
regions as follows.

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1 1 1 1 1 1
= + and = +
D M DAB Dk ( ) M
D m DAB Dk ( ) m

No tortuosity factor is involved in this model. The actual path length is equal to the
distance co-ordinate in the direction of diffusion.

For a pellet containing only macropores, substituting ε m = 0 in equation (6) gives

De = D M ε M2 .

Similarly for materials with only micropores, putting ε M = 0 in equation 18 gives

De = D m ε m2

Effectiveness factor η

In a porous catalyst, the internal surface area within the pores constitutes the effective
surface on which the active metals are deposited. Hence, for reaction to occur, the
reactants need to travel through the pores to reach the active sites. If there is any
resistance in diffusion of the reactants through the pores, then both the activity and
selectivity of the process is affected. In the absence of any internal mass transfer
resistance within the pores the concentration of reactants can be assumed to uniform and
equal to the surface concentration. Hence, the rate of reaction will also be uniform across
the catalyst pellet and equal to the rate evaluated at surface conditions. However, in the
presence of diffusional resistance, concentration of reactants gradually decreases from the
surface towards the center of the catalyst pellet, resulting in a concentration gradient.
When this concentration gradient is large enough, significant variation in reaction rate
occurs within the pellet. The average rate within pellet will be less than the rate
corresponding to the surface concentration. As pellet size decreases, the effect of
intrapellet transport becomes less significant.

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Rate of reaction for the whole catalyst pellets at any time is defined with respect to outer
surface conditions in term of effectiveness factor η as :

Actual rate of whole pellet (rp ) = η× rate evaluated at outer surface conditions (rs )

actual rate of whole pellet r


or, η = p
rate evaluated at outer surface conditions rs

Actual rate of whole pellet rp takes intrapellet mass transfer effects if any into account.

Effectiveness factor at isothermal conditions

For an irreversible first order reaction A → B, at isothermal condition the rate at surface
condition can be written as rs = k1CS . Then the actual global rate at outer surface

condition, rp =ηrs =ηk1CS .

For a spherical catalyst pellet of radius ‘Rs’, mass balance over a spherical shell volume
of thickness ∆R at steady state will be :

(Rate of diffusion of reactant into element) – (Rate of diffusion of reactant out of


element) = Rate of disappearance of reactant within element due to reaction

Rate of reaction per unit mass of catalyst = k1C

Rate of reaction per unit volume of catalyst = k1Cρp .

Where ρp is the density of pellet.

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Then the mass balance equation over the element of thickness ∆R can be written as

 2 dC 
R
 2 dC 
 −4πR De dR  −  −4πR De dR 
R +∆R
= ( 4πR ∆R ) ρ k C
2
p 1

If limit is taken as ∆R → 0 and assuming that effective diffusivity is independent of


concentration of reactant the above equation can be written as

d 2C 2 dC k1ρp
+ − C=
0 (7)
dR 2 R dR De

Boundary conditions :

dC
At the center of the pellet, = 0 at R = 0 (8)
dR

At outer surface C = Cs at R = R s (9)

Solving the differential equation (7) with boundary conditions (8) and (9) following
relation is obtained

C R s sinh ( 3ϕs R / R s )
= (10)
CS R sinh 3ϕs

Where ϕs is a dimensionless group defined as

R k1 ρp
ϕs = s
3 De

The ϕs is called Thiele modulus for spherical pellet. Equation (10) gives the
concentration profile of A in the pellet.

This concentration profile is used to evaluate the rate of reaction rp for the whole pellet.

Calculating the diffusion rate of reactant into pellet at position R s per unit mass of
catalyst pellet

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1  dC 
=
rp 4πR s2 De   (12)
mp  dR R =R s

4
mP = πR s2ρp = mass of pellet
3

Substituting the value of mp in equation (12)

3  dC 
rp = De  
R s ρp  dR R =R s

or

rp 3  dC  3  dC 
η= = De   = De    rs = k1Cs (13)
rs R sρp ( rs )  dR R R=
= s
R sρp ( k1Cs )  dR R Rs

C R s sinh ( 3ϕs R / R s )
Differentiating = and evaluating the derivative at R = R s and
CS R sinh 3ϕs
substituting in equation (13), following relation for η can be obtained for isothermal
conditions.

1  1 1 
=η  − 
ϕs  tanh 3ϕs 3ϕs 

Then substituting the η in the rate for whole pellet in terms of concentration at outer
surface rp = η k1Cs , can be written as

1  1 1 
= −
ϕ s  tanh 3ϕ s 3ϕ s  1 s

rp kC

Where for spherical pellets of radius rs, ϕ s for a first-order reaction is given as

Rs k1 ρ p
ϕs = . (12)
3 De

k1 is rate constant, ρ p is pellet density; De is effective diffusivity.

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Hence, to calculate Thiele modulus, both effective diffusivity De and rate constant k1
need to be known. Fig 3 shows the typical plot of η vs φs.

Fig. 3. Typical plot effectiveness factor η as function of Thiele modulus φs

As the figure shows, for small values of ϕ s , η → 1 . Equation (13) shows that small

values of ϕ s are obtained when the :

1. pellets are small


2. diffusivity is large
3. reaction is intrinsically slow ( catalysts of low activity).
1
For ϕ s > 5 , η can be approximated as η= . For such large ϕ s , intra-particle
ϕs
diffusion has a large effect on the rate. At this condition, diffusion into the pellet is
relatively slow and reaction occurs before the reactant has diffused far into the pellet.

When η → 1 , rate for the whole pellet is the same as the rate at surface concentration Cs
and the entire catalyst surface is fully active.

When η << 1 , the concentration within pellets drops from Cs to nearly zero in a narrow
region near rs. At this condition, only the surface near the outer periphery of the pellet is

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effective and the catalyst surface in the central portion of the pellet is not utilized. This
situation can be caused by large particles, low De or high k1; that is very active catalysts.

Hence, low effectiveness factors are more likely with very active catalysts. More active
the catalyst, the more is the possibility that intrapellet diffusion resistance will reduce
global rate. For flat plate or slab of catalysts, opened to reactant only from one side with
all other surface being sealed to reactant, the effectiveness factor is given as

tanh ϕ L k1 ρ p
η= where, ϕ L = L and L = thickness of plate
ϕL De

If the slab is open to reactant on both side of the plate, the expression remains similar
with L becoming the half of the plate thickness.

Book Reference :

• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981


• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India., 1999
• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications, 2001
• O. Levenspiel , Chemical reaction engineering, John Wiley & sons, 1995

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Lecture 24

Significance of intrapellet diffusion

P.B. Weis has developed a criterion for detecting whether intrapellet diffusion may be
1
neglected. The basic assumption is that if ϕ S ≤ , then η → 1 .
3

1
When ϕ S ≤
3

Rs k1 ρ p 1 Rs k1 ρ p
Or ≤ ϕ s =
3 De 3 3 De

Rs2 k1 ρ p
Simplifying and squaring , ≤1
De

rp rp
Now=
k1 = , where rp is the measured rate and η → 1 .
ηC s C s

Rs2 ρ p rp
Substituting k1 , ≤ 1 . This is known as the Weisz Criteria.
De C s

This criterion can be approximately used for most catalytic kinetics though it is derived
Rs2 ρ p rp
st
for a 1 order reaction. Hence, if criterion ≤ 1 , is fulfilled then η → 1 and there
De C s
is no intrapellet diffusion limitation.

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Effect of intrapellet mass transfer on activation energy

Neglecting intrapellet mass transfer can lead to misleading conclusions about reaction
activation energies.

1
At ϕ s > 5 , η ≅
ϕs

Rs k1 ρ p
For 1st order reaction, ϕ s = ,
3 De

3 De
Or η =
Rs k1 ρ p

Then the rate of the whole pellet can be written as

3 De 3C s k1 De
=rp η=
k1C s =
k1C s
Rs k1 ρ p Rs ρp

Substituting k1 = A1e − E1 / RT , where E1 is the true activation energy.

3C s A1e − E1 / RT De
rp =
Rs ρp

1/ 2
3C s  De 
rp =   A11/ 2 e − E1 / 2 RT (1)
Rs  ρ p 

Now if intrapellet resistance is neglected then the rate of first order reaction is given
as

− E 1' / RT
=
rp k=
1C s A1' e Cs (2)

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Here A' and E ' are apparent frequency factors and apparent activation energy,
respectively. Then comparing (1) and (2)

E1
E1' = ( 3)
2

Thus apparent activation energy is actually half of true activation energy. When
internal mass transfer resistance is not considered than the activation energy obtained
will be half of the actual value. These conclusions are same for all reaction orders.

However it should be kept in mind that relation (3) is true only at isothermal
condition and effective diffusivity is constant. If temperature varies then effective
diffusivity changes and for large ϕ s the apparent activation energy is given as

E1 + Ediff
E1' = . Under this condition, if the activation energy for diffusion (Ediff) is
2
E1
much less than the activation energy of the reaction, Ediff << E1 then only E1' = .
2

In the plot of ln k vs 1/T , at low temperature the data would give a line with slope
equal to –E/R as η → 1 . At high temperature intrapellet diffusion is important and
line with slope –E/2R will be obtained.

Equation 3 shows that rate rp is inversely proportional to pellet size Rs. If intrapellet
diffusion is insignificant, the rate is independent of pellet size.

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Effect on order of reaction

For a nth order reaction ,Thiele modulus is given as

R kn ρ pC sn−1
ϕn = s
3 De

1
For significant intra-pellet diffusion limitations , η =
ϕs

3 De
η=
Rs kn ρ pC sn −1

The rate is given as

( n + 1)
=( )
rp
n
η=
knC
3
Rs
n
s
De
kn ρ pC s
n −1
=
knC sn
3
Rs
De
ρp
k 1/ 2
n C s
2
(4)

If intrapellet diffusion is not considered the rate can be written as

(r ) = knC sn
'

p (5)
n

Here n ' is called the apparent order. Comparing equation (4) and (5)

n+1
n' = Here, n is the true order
2

When n=0 , n′=1/2

n=1 , n′=1

n=2 , n′=3/2

The above relations shows how due to presence of pore diffusion limitations, for zero
order and second order reactions, the apparent reaction order appear reduced.

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Solved examples:

Dehydrogenation of hydrocarbon (mol.wt = 58) at atmospheric pressure was carried out


over chromia-alumina catalysts at 530 0C. The reaction follows a first order kinetics with
rate constant of 0.94 cm3 /s. g cat. The spherical catalysts are of 30 mm diameter and
average pore radius is 11 nm. Pellets have porosity of 0.35 and density of 1 gm/cm3.
Assume Knudsen diffusivity to be dominant. Predict an effectiveness factor for the
catalysts. Use parallel pore model with a tortuosity factor of 3.0

1/2
 T 
Knudsen diffusivity is given as : ( Dk )=
A
9.7 ×10 a 
3

 MA 
Solutions :

Density of catalysts pellets = 1 gm/cm3 , T= 530 0C; Dp= 0.3 cm ; Rs= 0.3/2 = 0.15 cm

k1= 0.94 cm3 /s. g cat ; a=pore radius = 11 nm = 11 × 10-7 cm

δ=3 ; ε = 0.35

1/2
 T 
( Dk )=
A
9.7 ×10 a 3

 MA 

MA=58 ; a = 11 nm = 11 × 10-7 cm ; T= 530 0C = 530 + 273 = 803 K

1/2
 803 
( Dk ) A = 9.7 ×10 ×11×10 
3 −7 2
 = 0.0397 cm /s
 58 

εD
De =
δ

D=DK= 0.0397 cm2/s ; δ = 3 , ε = 0.35

ε D 0.35 × 0.0397
=
De = = 4.63 ×10-3 cm2/s
δ 3

Rs k1 ρ p 0.15 0.94 ×1
=ϕs = = 0.712
3 De 3  4.63 ×10−3

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1  1 1  1  1 1 
=η  −=  − =
ϕ s  tanh 3ϕ s 3ϕ s  0.712  tanh(3 × 0.712) 3 × 0.712 
 0.786

Effect of internal mass transport on selectivity

Selectivity of a product can be defined as the ratio of global rates for formation of
different products at that point. Combined effect of external and internal diffusion
resistances on selectivity at isothermal conditions are discussed below.

1. Independent and parallel irreversible first order reactions


A 
k1
→B B desired product
R 
k2
→S

It is further assumed that:

1. k1 > k2
2. Isothermal condition
3. Both external and internal diffusion resistances affect the rate.

At steady state , rate for catalyst pellet can be written as

=rp km am ( Cb − Cs ) (6)

am = external area for masstransfer per unit mass of catalysts


Cb = bulk concentration
Cs = surface concentration

The rate for catalyst pellet can also be written as rp = η k1Cs (7)

Eliminating surface concentration Cs between equations (6) and (7)

1
rp = Cb
1 1
+
km am η k1

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Thus external effect can be treated as a separate additive resistance. The reduction in rate
due to internal diffusion resistance through η is combined with rate constant k for
chemical steps.

If there is only internal mass transfer resistance then Cs= Cb

1
Say ϕ s ≥ 5 , hence η =
ϕs

1
rp =
ηk1Cs =k1C b  Cs = C b
ϕs

3 k 1D e
Or rp = Cb
Rs ρp

Then selectivity of B is given as

rp1 k1 ( D e ) A ( Cb )A
S= =
k 2 ( De )R ( Cb )R
B
rp2

If differences in diffusivities are neglected ( De )A ≈ ( De )R

k1 ( Cb )A
SB = (8)
k2 ( Cb )R

In absence of internal mass transfer resistance selectivity of B is given as

rp1 k1 ( Cb ) A
S= = ( 9)
k2 ( Cb ) R
p
rp 2

Comparison of equations (8) and (9) shows that the intrapellet diffusion resistance
reduces the selectivity.

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(2) For parallel irreversible first order reaction with same reactant. B is desired.

A 
k1
→B
A 
k2
→C

rp1 k1 ( Cb ) A k1
S= = = .
k2 ( Cb ) A k2
B
rp 2

Hence at this condition selectivity of B is unaffected by internal transport effect.

(3) For irreversible first order consecutive reaction

A 
k1
→ B 
k2
→C

Here B is the desired product. The selectivity of product B with respect to reactant A is
can be expressed as

net rate of production of B


SB =
rate of disappearance of A

dCB k C − k 2CB k C
or SB = = 1 A = 1− 2 B (10)
−dCA k1CA k1CA

The CA and CB are bulk concentrations of A and B respectively. The equation (10) gives
selectivity of B for whole pellet provided that the internal diffusion resistance is
negligible. In presence of significant intrapellet diffusion resistance, the concentration of
CA and CB changes within the pellet and the selectivity will vary with the position within
the pellet as CB/CA changes. Diffusion resistance causes CA to decrease from outer
surface to the center of pellet. The product B is formed within pellet and has to diffuse
out from the pellet into bulk. Hence concentration of B increases toward center of pellet
due to resistance. Hence from equation (10) it can be seen that decrease of CA and
increase of CB toward center of pellet result in reduction of pellet selectivity for B from
centre to outer surface. For the given first order reaction in presence of strong diffusion
resistance (say η ≤ 0.2 ) and assuming equal effective diffusivities, the selectivity of B
can be obtained as

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( k1 / k 2 )1/2 −  k 2 
1/2
CB
=SB 1/2   (11)
1 + ( k1 / k 2 )  k1  CA

Comparison of equations (10) and (11) shows that the selectivity is significantly reduces
when internal diffusional resistance is significant.

Book Reference :

• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981


• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India, 1999
• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications, 2001
• O. Levenspiel , Chemical reaction engineering, John Wiley & sons, 1995

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Lecture 25

Catalyst deactivation

Activity of catalysts normally decreases with time. The life of any catalyst generally
depends on type of reactions as well as reaction conditions. For example, catalysts for
catalytic cracking lose much of their activity within seconds due to carbon deposition on
the surface while promoted iron catalysts used in ammonia synthesis have a lifetime of
years. For any catalytic process, the life of catalyst is a major economic factor. To
regenerate or replace deactivated catalysts, the process needs to be shutdown and
consequently production is disrupted. Subsequent separation and regeneration of catalysts
also involve time and cost. Therefore, deactivation of catalysts increases the cost of
production significantly. Hence, any catalytic process will be economically viable only if
regenerations are required infrequently and can be done inexpensively. A catalyst can be
deactivated in three ways

I. Poisoning
II. Fouling
III. Sintering or phase transformation
I. Poisoning
Poisoning basically involve chemisorption of reactants or products or feed impurities on
the active sites of the catalyst surface, thereby decreasing the number of active sites
available for catalytic reactions. Since poisoning involves chemisorptions, it is known as
chemical deactivation. This process can be reversible or irreversible. Compound of
sulphur and other materials are frequently chemisorbed on nickel, copper and Pt catalysts.
In reversible poisoning, the strength of adsorption bond is not great and activity is
regained when the poison is removed from the feed. When the adsorbed material is
tightly held on the active sites, poisoning is irreversible and permanent.

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II. Fouling
Rapid deactivation can be caused by physical deposition of substance on the active sites
of catalysts. Carbon deposition on catalysts used in petroleum industry falls in this
category. Carbon covers the active site of the catalysts and may also partially plug the
pore entrance. This type of deactivation is partially reversible and regeneration can be
done by burning in air.

C →
air / high temperature
CO / CO2

III. Sintering or phase transformation


Because of local high temperature, support of catalysts or catalyst itself may undergo
structural modification or sintering causing a reduction in specific surface area or change
in chemical nature of catalytic agent so that it becomes catalytically inactive. Hence,
poisoning and fouling are dependent on concentration of reactant or product or
impurities. On the other hand, sintering and phase transformation may be assumed to be
independent of fluid phase composition. This is also therefore known as independent
deactivation.

Steps to reduce deactivation: Following steps can be taken to reduce the possibility of
deactivation of catalysts :

a. Removal of poison material form feed


b. Use of hydrogen which reduces coking
c. Removal of hot spot by proper design of reactor /process control to
prevent any thermal deactivation.

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Mechanism of catalysts deactivation

The deactivation of catalysts can occur by different mechanism as explained below :

1. Parallel deactivation
Reactant (A) produces a side product (P) which can deposit on the surface thereby
deactivating it. Deposition depends on reactant concentration.

R
A
or A→ R+ P ↓
P↓
2. Series deactivation

Reaction product (R) can decompose or react further to produce material (P) that
deposits and deactivates the surface. In this case, deposition depends on product
concentration.

A→ R→ P ↓

3. Side-by-side deactivation
In this mechanism, impurity in feed (P) deposits on the surface deactivating it. Deposition
depends on concentration of impurities in the feed.

A→ R
P→P↓

4. Independent deactivation
This catalyst decay involves structural modification or sintering of catalyst surface
caused by exposure of catalysts to extreme conditions such as high temperature. This
decay is dependent on time that the catalyst spends in high temperature conditions and is
independent of the materials in the fluid.

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Deactivation kinetics

Activity of catalysts pellet at any time is defined as

rate at which the pellet converts reactant A − rA'


a =
rate of reaction of A with fresh pellet − rA' 0

Reaction rate can be considered as function of temperature, reactant concentration and


present activity of the catalysts pellet. Therefore for nth order reaction, rate can be written
as

− rA' =
kC An a

where a is the present activity of the catalyst.

Similarly, deactivation rate can be considered as function of temperature, concentration


of substance that deactivates the catalyst (which can be reactant, product or impurities)
and present activity of the catalyst pellet. Hence, deactivation rate can be given as,

da
− =
kd C in 'a d
dt

i = A (reactant), R (product) , P(3rd substance)

Here d is called order of deactivation, kd is deactivation rate constant and n΄ is the


concentration dependency.

Deactivation rate for different types.

1. Parallel , A → R + P ↓
Reaction rate is − rA' =
kC An a

da
Deactivation rate is − =
kd C An 'a d d = order of deactivation
dt

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2. Series A → R → P ↓
Reaction rate is − rA' =
kC An a

da
Deactivation rate is − =
kd C Rn 'a d
dt

A→ R
3. Side-by-side deactivation ,
P→P↓
Reaction rate is − rA' =
kC An a

da
Deactivation rate is − =
kd C Pn 'a d
dt

4. Independent deactivation
Reaction rate is − rA' =
kC An a

da
Deactivation rate is − =
kd a d
dt

Deactivation kinetics for sintering

Most commonly used decay law for sintering is second order with respect to present
activity.

da
rd =
− =
k d a2
dt

The kd is the sintering decay constant. Integration with a=1 at time t=0 gives

1
a(t) = (1)
1 + k dt

Activity can be measured in terms of amount of sintering. If the total active surface area
of the catalyst is Sao at t = 0 and Sa at any time t, then activity can be written as

Sa
a(t) = (2)
Sao

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From equation (1) and (2)

Sao
Sa =
1 + k dt

The sintering decay constant kd is given as

 E  1 1 
=k d k d (To )exp  d  −  
 R  To T  

Ed is the decay activation energy. For reforming of heptanes on Pt /Al2O3 value of Ed is in


the order of 70 kcal/mol.

Deactivation kinetics for coking or fouling

Various empirical relations are available for calculation of amount of coke deposited on
catalyst surface after a time t.

Cc = At n (3)

Cc is the concentration of carbon on the surface in g/m2. The ‘n’ and ‘A’ are fouling
parameter functions of feed rate. Representative value of A and n for cracking of light gas
oil is 0.47 and 0.5 respectively when ‘t’ is in minute.

The activity can be related to amount of coke deposited on the surface by following
relation :

1
a=
1 + k cCpc

Substituting value of Cc from relation (3), in term of process time, activity can be
expressed as shown below.

1 1 1
=a = =
( ) 1 + kcA t 1 + k 't m
p p np
1 + k c At n

or

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1
a=  t in seconds
1 + 7.6t1/2

Other dimensionless fouling correlations are also developed by several groups.

Deactivation kinetics for poisoning

For petroleum feed containing trace impurities such as sulfur, the poisoning reaction can
be written as P + S → PS

The rate of deactivation is given as

da
rd =
− =
k 'dCm
pa
q
dt

The Cp is the concentration of poison in feed. The ‘m’ and ‘q’ are respective orders.

The rate of removal of poison from the reactant by catalyst sites is proportional to the
number of sites that are not poisoned (Cto - Cps) and concentration of poisons in the gas
phase, Cp. The Cps is the concentration of poisoned sites and Cto is the total number of
fresh sites initially available. Then rate of removal of poison is equal to rate of formation
of poisoned site and is given as

( )
dCps
= r=
ps k d Cto − Cps Cp
dt (4)

Dividing throughout by Cto and if ‘f’ is the fraction of the total number of the sites that
have been poisoned then equation (4) can be written as

df Cps
k d ( 1 − f ) Cp
= f = (5)
dt Cto

The fraction of sites available for adsorption (1-f) is essentially the activity a (t). Then
equation (5) becomes

da
− =
at k dCp
dt

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Determination of deactivation kinetic parameters

Case 1 : Consider a reaction in a mixed reactor under constant flow condition. Let
independent deactivation occur. Assume both the main reaction and deactivation reaction
to be first order with respect to activity ‘ a ’.

Then,

Reaction rate − rA =
kC Aa (6)

da
Deactivation rate − =
kd a (7)
dt

Integrating equation (7)

da
−∫ kd ∫ dt
a t
=
a0 a 0

Or [ ln a ]a = − kd t
a
ao is initial activity
0

a a
ln = − kd t or = exp ( − kd t )
a0 a0

or =a a0 exp ( − kd t )

or exp ( − kd t )
a=  a0 =
1

W X
For mixed reactor , = A
FA0 − rA

Substituting expression for rate from equation (6)

W XA
=
FA0 kC Aa

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C A C A0 − C A
Now , X A =
1− =
C A0 C A0

W XA C A0 − C A
Hence, substituting for XA , = =
FA0 kC Aa kC A0C Aa

WkC A0 a C A0 − C A WkC A0 a C A0
Or = Or = −1
FA0 CA FA0 CA

C A0  WC A0 
Or −1 =ka  
CA  FA0 

C A0 WC A0
=
Or − 1 kaτ=
w τ w . (8)
CA FA0

τ w is called the weight time similar to space-time τ . CA and ‘ a ’ vary with time.

=
Substituting, a exp ( − kd t ) in equation (8)

C A0
Or = − 1 kτ w exp ( − kd t )
CA

C 
Or − 1 ln ( kτ w ) − kd t
ln  A0 =
 CA 

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C 
Plotting ln  A0 − 1 versus ‘t’ gives a straight line of slope of -kd and intercept
 CA 
ln ( kτ w )

Intercept = ln ( kτ w )

Slope = -kd
C 
ln  A0 − 1
 CA 

t
Fig. 1. Plot to determine the rate constant and the deactivation rate constant for a reaction over deactivating catalyst. ( For
mixed reactor, constant flow and independent deactivation)

Case II : Consider a reaction in a mixed reactor under changing flow condition so that
concentration is constant. Let parallel deactivation occur. Assume the main reaction to be
nth order and the deactivation reaction to be of first order in activity ‘a’.

R
A
Parallel deactivation
P↓
Rate equation − rA =
kC An a

da
Deactivation rate − =
kd C Am a d
dt

Since concentration is constant,

− r=
A kC An=
a k 'a  k=' kC An

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da
−= kd C Am=
a d kd' a d =
kd' kd C Am
dt

For mixed reactor ,

W X A X A C A0 − C A
= = =
FA0 − rA k 'a k 'aC A0

WC A0 C A0 − C A
Or =
FA0 k 'a

C A0 − C A WC A0
=Or τw = '
τ w (9)
ka FA0

da
Now , − =
kd' a d
dt

For first order activity , d =1

exp ( − kd' t )
Again , a =  a0 =
1

Then substituting ‘ a ’in equation (9)

C A0 − C A C A0 − C A C A0 − C A
=τw = =
k ' exp ( − kd' t ) exp ( − kd' t )
'
ka k'

C − C 
=
Or ln τ w ln  A0 ' A  + ln ( kd' t )
 k 

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C − C 
Plotting ln τ w versus ‘t’ gives a straight line of slope of kd' and intercept ln  A0 ' A  .
 k 

Slope = kd

ln τ w

 C A0 − C A 
Intercept = ln  
 t k' 

Fig. 2 . Plot to determine rate constant and deactivation rate constant for a reaction over deactivating catalysts for mixed
reactor, changing flow condition and parallel deactivation

Book Reference :

• O. Levenspiel , Chemical reaction engineering, John Wiley & sons. 1995


• R. J. Farrauto & C. H. Bartholomew, Fundamentals of Industrial catalytic Processes,
Blackie Academic & Professional, 1997
• H. S. Fogler, Elements of Chemical reaction engineering, Prentice Hall of India, 1999
• J. M. Smith, Chemical Engineering Kinetics, McGrawHill Book Company, 1981
• J.J. Carberry , Chemical and catalytic reaction Engineering, Dover Publications, 2001

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Lecture 26

Industrial catalytic processes

Industrial catalytic processes can be broadly classified into five major sectors as shown in
Fig. 1

Fig. 1. Classification of industrial catalytic processes

In this section, few representative processes will be discussed emphasizing on the catalyst
used, reaction kinetics and catalyst deactivation, if any.

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Steam reforming

Synthesis gas or hydrogen is produced most commonly by steam reforming of


hydrocarbons. Feed is mostly natural gas or naphtha. Overall process involves mainly six
catalytic steps :

1. Purification of hydrocarbons

2. Primary steam reforming

3. Secondary steam reforming

4. High temperature water gas shift reaction

5. Low temperature water gas shift reaction

6. Methanation

Fig 2 shows the schematic flow diagram for hydrogen production by steam reforming of
natural gas. The various catalytic steps are discussed below.

Purification of hydrocarbons

Sulfur and chloride compounds in the feed act as catalyst poisons. Therefore, before the
reforming process, feed is treated to remove these compounds. Sulfur is removed by
desulphurization followed by scrubbing by ZnO adsorbent. By this process, sulfur is
reduced to less than 0.01 ppm

R-S + H 2 →
CoMo / Al2O3
H 2S + R-H Hydrodesulfurization

H 2S + ZnO 
→ ZnS + H 2 O Scrubbing by adsorbent

Chloride is removed by scrubbing using alkali treated alumina to 5 ppb level.

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Steam Steam

Natural gas feed 350 0C 200 0C 300 0C


400 0C 800 0C

Hydrogen
800 0C 1000 0C

Desulfurization Primary Secondary High Low COx


temperature temperature methanation
Reformer Reformer
WGS WGS
Fig. 2. Schematic flow diagram for hydrogen production from steam reforming of natural gas

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Primary steam reforming

For steam reforming of natural gas, which mostly consists of methane, the overall
reaction is given as :

CH 4 + H 2 O =CO + 3 H 2 ∆H o298 K = + 206 kJ/mol

This reaction is always accompanied with methanation and water gas shift reaction.

Methanation CO + 3 H 2 = CH 4 + H 2O ∆H o298 K = - 206 kJ/mol


WGS CO + H 2O =CO2 + H 2 ∆H o298 K = - 41.2 kJ/mol

The overall process is endothermic and heat is supplied to the reformer. Relative amount
of H2 and CO can be adjusted by process conditions. Since the overall steam reforming
reaction is highly endothermic and the product volume is greater than that of the
reactants, equilibrium favors the forward reaction at high temperature and low pressure.
High steam to methane ratio and high temperature favors conversion of CH4. As
temperature is lowered, the slightly exothermic WGS reaction becomes increasingly
more favorable. Higher steam to methane ratios at lower temperature result in lower CO
concentration. The H2 to CO ratio thus depends on operating temperature for steam
reforming and water gas shift reactions.

Process

A schematic diagram depicting the typical reaction conditions in primary steam


reforming is shown in Fig. 3. For primary steam reforming, the outlet temperature is
limited to about 800 0C to prevent damage to the reactor. Though the reaction is
thermodynamically favored at low pressure, a higher pressure is used to increase the
reaction rate and throughput, thereby minimizing the reactor volume.

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Fig. 3. Schematic diagram showing steam reforming reaction conditions

Operating condition for methane and naphtha steam reforming are very different. For
methane steam reforming the reformer exit temperature is typically 800 -900 0C and

H2O : CH4 ratio is 1.8 -3. In naphtha steam reforming exit temperature is lower 600-800
0
C and H2O : C ratio is higher 2.5-4.5. In both cases pressure is maintained at 20-30 atm.

Catalysts

Bifunctional catalysts are needed for steam reforming reaction. Two catalytic functions
are :

– Metal site for dissociative adsorption of hydrocarbon

– Oxide site for dissociative adsorption of water

Oxide sites are generally located on the surface of the supports. Support also stabilizes
the well dispersed metallic phase. Because of the severe high temperature reaction
conditions, catalyst must have high thermal stability. The typical decreasing activity
order for metals is Rh, Ru > Ni> Pd, Pt >Ni-Cu >Co. This order varies with hydrocarbon.

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Pt and Pd are less active than Ni for steam reforming of naphtha, however are more
active than Ni for steam reforming of toluene. Noble metals are more resistant to carbon
deposition and more tolerant to sulfur poisoning than Ni. However, because of greater
availability and lower cost, Ni is the preferred metal catalyst for commercial applications.
Thermally stable supports of low acidity are needed to prevent deactivation by sintering
and carbon depositions.

The order of decreasing acidity of supports:

SiO2-Al2O3 > SiO2-MgO> SiO2>>Al2O3>TiO2>ZrO2 >CaO, MgO

Thus CaO, MgO are most desirable supports to prevent carbon depositions. These are
also among most thermally stable supports. Promoters such as ‘potassium alumino -
silicate lower the acidity of supports and catalyze carbon gasification with steam.

Typical catalysts for steam reforming consist of NiO / Ca Al2O4 or NiO / Al2O3. Steam
reforming catalysts are chemically and mechanically rugged to maintain physical and
chemical integrity in harsh high temperature and high steam environment. Surface area of
carrier is low, typically 5-50 m2/g but adequate for dispersing NiO and maintaining
thermal stability. Support is impregnated with nickel nitrate solution a number of times
to achieve proper loading. Active catalyst is metallic Ni. Therefore, NiO after
calcinations, is reduced by H2 prior to reaction. Catalysts are formed into relatively large
Raschig rings, grooved pellets, wheels etc. for low pressure drop and minimum pore
diffusion limitations.

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Table 1. Activation energies reported for steam reforming process over various catalysts

Catalyst Activation energy Reaction Reference

kJ/mol

Rh/Ceα Zr1-α O2 84 Methane steam reforming 1

Rh/Ga-Ce 92 1

Rh/γ-Al2O3 109 1

Cu/ZnO/Al2O3 101 Methanol steam reforming 2

Ni-based catalyst 96 Methane steam reforming 3

Kinetics and mechanism

Mechanistically, steam reforming involves decomposition of hydrocarbons on metal


surface to hydrocarbon fragments. Water undergoes dissociative adsorption to adsorb
oxygen atoms and molecular hydrogen. Adsorbed oxygen atom combines with adsorbed
hydrocarbon to form CO. The kinetic model proposed by Rostrup and Nielsen [4] is as
follows

m−z
C n H m + 2 S 
kA
→ C n H z − S2 + H2
2
C n H z − S2 + nS 
kH
→ C n−1 H z' − S2 + CH x − Sn
x
CH x − Sn + O − S 
kr
→ CO + H + ( n + 1) S
2 2

H 2O + S 
W

 O − S + H2
K


H 2 + 2 S 
KH

 2H − S

The corresponding rate was derived as

k A pcn H m
r= 2n
 nk A pH 2  pH O  
1 + pcn H m + KW  2  + k H pH 2 
 k r K W p H 2O  pH 
 2 

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Industrial steam reforming reaction is strongly influenced by pore diffusion resistance


and therefore apparent activation energies are lower compared to surface reaction
controlled system. Activation energy for nickel based catalyst for steam reforming
reaction 106 kJ/mol and that for water gas shift reaction 55 kJ/mol [5]. The effectiveness
factor is in the range of 0.05- 0.65 [5]

Deactivation

Sulfur and chlorides act as catalyst poisons. As mentioned earlier, the feed is initially
pretreated for sulfur and chloride removal. Another major source of deactivation is coke
deposition on the catalyst. Formation of carbon occurs by decomposition of hydrocarbon
and CO on the surface of catalysts

→ nC + ( m / 2 ) H 2
Cn H m 
2CO 
→ C + CO2

Gas phase non catalytic pyrolysis of hydrocarbons also contributes to coke deposition.

All of these processes are favored at high temperature. High temperature also results in
sintering, growth of metal crystallites and collapse of catalyst support which can cause
decrease in activity.

Carbon can be removed by steam gasification. Carbon deposition can be avoided by


operating at sufficiently high H2O to C ratio.

Secondary steam reforming

The exit gas from the primary reformer contains about 10-13 % CH4 which is further
reformed in secondary reformer. Inlet temperature is 800 0C and the outlet temperature is
900-1000 0C. These high temperatures drive the forward reaction and reduce the CH4
content to less than 1%. Outlet CO concentration is 10-13 %. Reactor is lined with
ceramic material to prevent damage.

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Catalysts

Catalyst must be able to withstand the severe high temperature. Typical catalysts are Ni
supported on alumina or CaO substituted alumina. Potassium is not added due to
volatility at this high temperature. Total BET surface area and surface area of active
nickel for secondary reforming catalysts are smaller than that of primary reforming
catalysts. This is because they are initially calcined at high temperature so that they are
thermally stable at process conditions.

Water gas shift reaction

Water gas shift reactions are carried out at conditions of high and low temperature. For
the water gas shift reaction, the equilibrium favors the reaction at lower temperature.
However, copper based catalyst, active at low temperature, is highly sensitive to residual
sulfur or chloride compounds which have passed through the pre-purification steps.
Hence, initially the reaction is carried out over catalyst composed of Fe2O3 and Cr2O3
which is relatively inexpensive, resistant to sintering and tolerant to sulfur and chloride
poisoning. However, at low temperature Fe3O4 is not sufficiently active hence, the
reaction has to be carried out at higher temperature. The high temperature catalyst
adsorbs the residual sulfur or chloride compounds thereby, protecting the low
temperature copper based shift catalyst from exposure to these compounds. The high
temperature process is followed by shift reaction at thermodynamically favorable lower
temperature of 200 oC over copper based catalyst.

High temperature water gas shift reaction

Gas from the secondary reformer contain 10-13 % CO and is further processed to
increase the H2 concentration. The high temperature water gas shift reaction lowers the
CO concentration to about 2-3 % in a fixed bed reactor.

CO + H 2O =CO2 + H 2

Process is operated at 350-500 0C and 20 -30 atm. Since equilibrium favors the WGS at
lower temperature, the feed gas is cooled to 350-400 0C before entering the reactor.

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Catalysts :

A typical catalyst is composed of 90 % Fe3O4 and 10 % Cr2O3. Fe3O4 acts as the active
metal while Cr2O3 acts as a stabilizer to minimize sintering of the active iron oxides. The
catalysts are prepared by precipitation.

Kinetics

The rate expression from Langmuir Hinshelwood model proposed is given as [4] :

( )
2
kK CO K H 2O PCO PH 2O PCO2 PH 2
r=
(1 + K )
2
CO PCO + K H 2O PH 2O + K CO2 PCO2 + K H 2 PH 2

k is the rate constant and Ki’s the respective adsorption constants. The ‘i’ represents the
chemical species.

Activation energy for the water gas shift reaction on iron oxide/chromia is in the range of
122 kJ/mol. Reaction over small pellets (5 × 4 mm) operates with an effectiveness factor
of unity below 370 0C and 31 atm.

Deactivation

The catalyst is deactivated by adsorption of residual S or Cl containing compounds that


escape the initial purification steps.

Low temperature water gas shift

The CO concentration of the existing gas from high temperature WGS is 2-3 % and

further reduced to below 0.2 % by low temperature water gas shift reaction. The WGS
reaction as favored at low temperature, operating temperature is maintained at 200 0C, the
minimum temperature at which steam is not condensed and operating pressure at 10-30
atm.

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Catalysts

A typical catalyst is composed of CuO/ ZnO/Al2O3 and prepared by co-precipitation


method. The catalyst is highly selective for shift reaction with low activity for
methanation reaction. CuO is the catalytically active metal and ZnO minimize sintering
of Cu. Cu is highly sensitive to poisoning by S or Cl compounds even at very low level of
1 ppm. ZnO & Al2O3 also scavenge the S or Cl compounds protecting Cu which is
highly sensitive to poisoning by these compounds. Catalyst is reduced very carefully by
H2 and the bed temperature is never allowed to rise above 230 0C to avoid sintering of
Cu. The high temperature shift catalyst also protects the low temperature catalyst from
these poisons.

Kinetics

Kinetic model is based on surface redox mechanism involving dissociation of water to


OH radicals which further dissociate to atomic oxygen. The rate expression as proposed
by Ovensen et al.[2] is

 − Ea  m n 1 pCO2 pH 2
r A exp   pCO pH 2O=x
pCO p Hy ( 1 − β ) β
 RT  2 2
KWGS pCO pH 2O

A= pre-exponential factor; Ea= activation energies; m, n, x, y = respective reaction


orders; β defined as approach to equilibrium and KWGS is equilibrium constant for WGS
reaction.

Final CO/CO2 removal by methanation

After low temperature WGS, the CO content in hydrogen stream is 0.2-0.5 % and must
be reduced to 5 ppm level for using the H2 for ammonia synthesis. The CO is further
reacted with hydrogen and converted to methane. The catalyst is typically Ni/Al2O3 .
MgO is sometimes used as a promoter to minimize sintering of Ni. The process is carried
out at 300 -350 0C and at 30 atm pressure. Care must be taken to avoid formation of
poisonous Ni(CO)6 which occurs below 200 0C at partial pressure of CO greater than ~
0.2 atm.

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Book reference:

• C. H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic


Processes, Wiley, VCH, 2006

Publication reference:

1. M.H Halabi M.H.J.M de Croon, J. van der Schaaf, P.D. Cobden, J.C. Schoulen ,
Applied catalysis A Gen. 389 (2010) 80-91
2. J. Agrell, H. Birgersson, M. Boutonnet, Journal of Power Sources 106 (2002)
249–257
3. M. Zeppieri, P.L. Villa, N. Verdone, M. Scarsella, P. De Filippis, Applied
Catalysis A: General 387 (2010) 147–154

4. J.R . Rostrup –Nielsen , Catalysis Science and technology eds. J.R. Anderson and
M. Boudart, Springer –Verlag , Newyork,1984

5. T. Numaguchi and K.Kikuchi, Chemical Engineering Science 43(1988) 2295-


2301

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Lecture 27

Petroleum refining industry

Petroleum refining industry extensively involves heterogeneous solid catalytic processes.


The major catalytic processes are shown in Fig 1.

Fig. 1. Various solid catalytic processes in petroleum refining industries

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Catalytic cracking

Catalytic cracking of gas oil is among the most important catalytic processes and major
source of fuels. This process involves simultaneous occurrence of various reactions.
Some typical reactions in catalytic cracking process are shown in Fig. 2.

1. Large alkane cracking


a. C14 H 30 → C 7 H 16 + C 7 H 14

2. Dealkylation of branched aromatics


C 3H 7

+ CH2= CH - CH3

3. Naphthene cracking

+ 2 C2H4

4. Hydrogen transfer

+ CH2= CH - CH3 + CH3 - CH2 - CH3

5. Isomerization
CH2

CH2= CH – CH2 - CH3 CH2 - C - CH3

Fig. 2. Some typical reactions in catalytic cracking process

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Process

Usually catalytic cracking of gas oil is carried out at 500-550 0C at 2-3 atm pressure, in a
fluidized bed reactor. In the fluidized bed reactor, most of the cracking occurs in the
transport-line (riser). Catalyst to oil weight ratio is usually maintained at 4 -6 with
residence time of 2-6 seconds in the riser reactor. The gasoil feed stock is usually consist
of C20-C40 in the boiling range of 350 -550 0C. Catalyst circulation rate of about 6 ton/m3
of total feed is maintained for smooth operation. The schematic diagram of a typical
fluidized catalytic cracking reactor is shown in Fig. 3.

Catalyst

Common cracking catalysts are amorphous SiO2-Al2O3 and zeolites. Zeolites are
alumino-silicates with well- defined crystalline structures having molecular size pores
that give rise to its shape selective properties. Zeolites are discussed in detail in later
sections. The product distribution in catalytic cracking process also depends on the type
of catalyst. The SiO2-Al2O3 catalyst gives higher alkene yield while zeolite catalyst result
in higher aromatic yield.

The typical commercial cracking catalyst is a mixture of zeolite and SiO2 –Al2O3. The
catalyst can contain 3-25 wt.% zeoliteY. The zeolite is usually ion exchanged with rare
earth ions such as La+3 or Ce+3 to provide additional thermal stability. The balance of
mixture is SiO2-Al2O3, similar to the original amorphous cracking catalyst. The function
of acidic SiO2-Al2O3 is to crack the large feed molecules to a size which can diffuse into
the zeolite channels for further reactions. The alumino-silicate matrix also protects the
zeolite from poisons and attrition. The catalyst particles are of 40-100 µm in diameter
with pore sizes in the range of 8-10 nm. Surface area of the zeolite ranges from 600-800
m2/g, whereas, the surface area of the alumino-silicate matrix is in the range of 100-300
m2/g.

Additives are added to cracking catalyst and constitute about 5 wt. % of catalyst.
Commonly used additives include octane boosting additives such as ZSM-5, metal
passivators, SOx reducing agents, and CO oxidation catalyst. Addition of 1-3 wt. % of
ZSM-5 increases octane number while decreases gasoline yield. Nickel increases gas and

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coke selectivities while vanadium destroys the zeolite lowering the activity. These
undesirable effects of Ni can be minimized by adding a passivator such as a compound of
antimony and bismuth to the process stream to react selectively with the Ni to form a
catalytically inactive Ni-Sb or Ni-Bi species. These are added commonly as
organometallic solutions to the process stream.

Cracking products

Cyclone separator

Catalysts

Riser reactor

Gas oil + regenerated catalysts

Fresh catalysts

Fig. 3. Schematic diagram for catalytic cracking in Riser reactor.

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Mechanism and kinetics

Cracking reactions involve C-C bond rupture via formation of carbocations. Reaction is
catalyzed by acid sites on SiO2-Al2O3 and zeolites catalysts. Carbocations are formed on
Bronsted and Lewis acid sites of the catalysts. A typical mechanism for catalytic cracking
of alkane initiated by protonation is given below:

R1 − CH 2 − CH 2 − R2 + HZ  R1 − CH 2 − CH 3+ − R2 + Z −
R1 − CH 2 − CH 3+ − R2 
→ R1+ + CH 3 − CH 2 − R2
R1 − CH 2 − CH 3+ − R2 
→ R1 − CH 2 − CH + − R2 + H 2
R1 − CH 2 − CH + − R2 
→ R1+ + =
CH 2 CH − R2

A detailed micro kinetic model for gas oil cracking involve hundreds of elementary
reaction steps for which kinetic parameters are to be determined. Due to this complexity
of cracking process, the kinetic study of these reactions is extremely difficult. For
simplification, the reaction steps and products are combined into groups of species. These
groups are called lumps and each lump is considered as an independent entity. This is
known as lumped kinetic technique.

A three lumped model proposed by Wojciechowski and Corma [3] for gas oil cracking is
shown in Fig. 4. Simple parallel- series kinetic network involves reactions of gas oil to
gasoline /diesel (path 1) or to gases/coke (path 2). The gasoline and diesel can further
react to give gas and coke.

Gas Oil 
k1
→ [gasoline + diesel] 
k3
→ [gas +coke]

k2

Fig. 4. Three Lumped kinetic model for catalytic cracking of gas oil

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The corresponding reaction kinetics was proposed to be first order with respect to each
hydrocarbon component of the feed reacting by path 1 or 2.

To account for rapid catalyst decay, each of the rate constants was modified using a time
–on-stream functions:

G= Modified deactivation rate constants [G=(m-1)kd ]

m = true deactivation order

N =modified deactivation order = [1/m + 1]

W= refractory index accounting for difficulty of cracking residue as reaction progress

Upon substituting the modified rate constants for k1 and k2 into equations (1) and
inserting this expression in equation for plug flow and integrating, an expression was
obtained by Wojciechowski and Corma [ 3] which relates instantaneous conversion XA to
the time of reaction tf while accounting for volume expansion εA.

b = constant and P= catalyst to oil ratio

This above model although useful for modeling the kinetics of gas oil cracking, was
highly empirical and could not be generalized for kinetics of catalytic cracking.

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A five lump kinetic model (Fig 5a) was proposed to describe the gas oil catalytic
cracking (FCC) process by Ancheyta-Juárez et al.[4]. The model contained eight kinetic
constants, including one for catalyst deactivation. The model included unconverted gas
oil, gasoline, LPG, dry gas and coke as lumps. The activation energies of the various
steps were in the range of 9-13 kcal/mol. Even seven lump kinetic models for fluid
catalytic cracking, as shown in Fig. 5b, are reported in literature. The shown seven-lump
model involved residual oil, heavy lump, light lump, gasoline, liquefied petroleum gas,
dry gas and coke [5]. The VGO, HFO and LFO in Fig 5b are vacuum gas oil, heavy fuel
oil and light fuel oil respectively.

Deactivation

The major sources of catalyst deactivation are

1. Coke formation
2. Deactivation by metals such as Ni, V
3. Sintering
Coke formation on the catalyst surface is the major deactivation source for catalytic
cracking catalysts. Very high rate of coke formation results in very low residence time of
catalysts in the reactor and high regeneration frequency. The metal residue in the feed can
also affect the performance and activity of the catalysts. Nickel increases gas and coke
selectivities while vanadium is reported to destroy zeolites and lowers the activity. The
effects of metals can be prevented by adding metal passivators. Antimony or bismuth
compound can be added which form Ni-Sb or Ni- Bi alloy. Magnesium orthosilicate is
also added to form MgO-V2O5-SiO2 . At severe conditions of high temperature and
steam, zeolite structure gradually deteriorates.

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Fig. 5. Lump kinetic models for catalytic cracking (a) Five lump kinetic models [4] (b) seven lump kinetic models [5]

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Hydrocracking

This process has wide range of applications including upgradation of petrochemical


feedstock, improvement of gasoline octane number, production of high quality lubricants
etc. The process upgrades the original feedstock by increasing its overall hydrogen-
to-carbon ratio and decreasing the average molecular weight.

Hydrocracking is extensively used for simultaneously cracking and hydrogenating low


value gas oil, containing high amount of cyclic polyaromatic and naphthenic compounds,
to produce high value products such as gasoline, diesel or jet fuel. Hydrocracking
involves multiple reactions such as ring opening, cracking, dealkylation and
isomerization with simultaneous saturation due to presence of hydrogen. The major
advantage of this process is higher selectivity towards cracking of polyaromatics to
desired fuels such as gasoline, diesel or jet fuel and less production of lower
hydrocarbons. This is in contrast with catalytic cracking process which gives rise to
considerable amount of lower alkene products. Some of the typical reactions are shown in
Fig. 6.

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(A)
C6H13 C6H13

2H2

C2H5
C2H5

4H2

C 2H5
H13C 6
+

C 2H5

C 2H5

+ C 6H 14

(B)

C 3H 7

C H2 C H3
H2
C 3H 8

3H2

C H2 C H3
C H2 CH 3
C 2H5 H2

H2

C H3
C 4 H 10

Fig. 6. Typical hydrocracking reactions

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Process

The process is typically carried out in a series of fixed bed reactors at 300-450 0C and
100-200 atm. The process is associated with large heat release due to exothermic
hydrogenation reactions which dominate the endothermic cracking reactions. The major
disadvantage of the process is the requirement of very high pressure of hydrogen with
large energy consumption making the process rather expensive. A typical two-stage
hydrocracker is shown in Fig. 7. In first stage 40-50 vol% of the feed is hydrocracked.
The first stage also acts as a hydrotreater , where poisonous nitrogen and sulfur
compounds are partially hydrogenated. The effluent from the first stage reactor
passes through heat exchangers to a high pressure separator where hydrogen-rich
gases are separated and recycled. The liquid from the separator is fed to a
fractionating tower and the tower bottoms form the feed to the second stage.
Usually fixed-bed reactors with liquid down flow are used.

Fig. 7. Schematic diagram of two stage hydrocracking process

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Catalysts

The hydrocracking catalyst has to be a bi-functional catalyst :

– Acid sites to catalyze cracking reactions

– Metal sites catalyzing hydrogenation

Catalyst choice depends on the nature of feed and desired product distribution. CoO-
MoO3-Al2O3 has been widely used for hydrocracking of heavy feed stocks such as
residual raffinate, solvent deasphalted residual oil and vacuum residue. Base metals
(Co, Mo, Ni, W) supported on Al2O3-SiO2 and zeolite are used for producing lubricating
oils and middle or heavy distillate. Typical catalysts consist of 2% Co 7 % Mo, 6% Ni,
20% W on Al2O3-SiO2 . The Ni/SiO2-A12O3 increased conversion of heavy polynuclear
compounds in the feed. Pt or Pd supported on zeolites are used for clean and pretreated
feeds and are highly selective towards gasoline, diesel or jet fuel. Typical catalyst is 0.5
wt % Pt or Pd on zeolites prepared by ion exchanges. Ni-Mo-zeolite and Ni-W-zeolite
catalysts are used for maximizing gasoline and gas oil production respectively. The Ni-
W-impregnated rare earth exchanged X-type zeolite was found to be more resistant
to nitrogen and structurally more stable. Catalyst poisoned by deposition of coke and
other materials is usually regenerated by burning off the deposits.

Mechanism and kinetics

As discussed earlier hydrocracking of petroleum feedstock also involves a complex


network of reactions of large number of components. Reviews [6, 7] on kinetics of
hydrocracking of heavy oil fractions include various lumped kinetic models. Callejas and
Martinez [8] for hydrocracking of residue over Ni-Mo/γ-Al2O3 catalyst in CSTR at 12.5
MPa hydrogen pressure and 375-415 oC temperature, used three lumps model (Fig 8a).
The three lumps were atmospheric residue (AR), light oils (LO) and gases. The kinetics
of hydrocracking of vacuum distillates was studied by Orochko et al. [9] over an
alumina–cobalt molybdenum catalyst using a first-order kinetic scheme as shown in
Figure 8b. The rate of a first-order heterogeneous catalytic reaction was expressed by the
following equation:

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where α = rate constant, t = reaction time, y = total conversion and b = inhibition factor
due to adsorption reaction products on catalysts.

Sanchez et al. [10] proposed a five lump kinetic model (Fig 8c) for moderate
hydrocracking of heavy oil in a fixed bed downflow reactor over Ni-Mo/ Al2O3 catalyst.
The lumps were unconverted residue, vacuum gas oil, distillates, naphtha, and gasses.
The model included 10 kinetic parameters. Krishna and Saxena [11] reported a detailed
kinetic model with seven lumps (Fig 8d) considering cuts of different temperatures. The
lumps were sulfur compounds, heavy and light aromatics, heavy and light naphthenes,
heavy and light paraffins. The pseudo components were considered light if they were
formed from fractions with boiling points lower than the cut temperature. Sulfur
compounds were considered to be a heavy lump.

Deactivation

Catalyst deactivation mainly occurs by deposition of coke on catalysts surface that can be
removed by periodic burn-off. The other source of deactivation is presence of sulfur and
nitrogen metals in feed. The S and N metals can be removed by feed pretreatment.

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Fig. 8. Various lumped kinetic models for hydrocracking reactions (a) Three lump model [8] (b) Four lump model [9] (c) Five
lump model [10] (d) Seven lump model [11]

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Book reference:

• C. H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic


Processes, Wiley, VCH, 2006

Publication reference :

1. L. Lloyd, D.E. Ridler, M.V. Twigg, Catalysts Handbook, ed M.V. Twigg Wolfe,
Chap6, pp 283-338
2. C.V. Ovensen, B.S. Clausen, B.S. Hammershøi, G. Steffensen, T. Askgaard, I.
Chorkendorff, J.K.Nørskow, P.B.Rasmussen, P. Stoltze, P.Taylor J. Catal. 158
(1996) 170-180
3. B.W. Wojciechowski, A. Corma, Catalytic cracking , catalysts chemistry and
kinetics , Marcel Dekkar, New York ,1986
4. J. Ancheyta-Juárez , F. López-Isunza ,E. Aguilar-Rodríguez, Appl. Catal. A:
General 177 (1999) 227-235
5. M. Heydari, H. AleEbrahim, B. Dabir, Amer. J. of Appl. Sci. 7 (2010) 71-76
6. S. Mohanty, D. Kunzru, D. N. Saraf, Fuel, 69 (1990)1467
7. J. Ancheyta, S. Sánchez, M. A. Rodríguez, Catalysis Today 109 (2005) 76–92
8. M. A. Callejas, M.T. Martínez, Ind. Eng. Chem. Res. 38 (1999) 3285–3289
9. D.I. Orochko, Khimiya I Tekhnologiya Toplivi Masel 8 (1970) 2–6.
10. S. Sánchez, M. A. Rodríguez, J. Ancheyta, Ind. Eng. Chem. Res., 44 (2005) 9409–
9413
11. R. Krishna, A. K. Saxena, Chem. Eng. Sci.44 (1989) 703–712.

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Lecture 28

Naphtha reforming

Naphtha is a 70-200 0C petroleum cut containing C5-C10 hydrocarbons. Naphtha feed


mainly consist of alkanes and naphthenes or cyclo-alkanes with very low amount of
aromatics. Naphtha reforming involves conversion of normal alkanes and cycloalkanes to
branched alkanes and aromatics to produce high octane gasoline and aromatic source for
chemical production.

The main reactions are dehydrogenation, isomerization and dehydrocyclization. The


dehydrocyclization of alkanes needs to be maximized for increase in aromatic production
but it is also the most difficult reaction to be accomplished. Typical examples of catalytic
hydrocarbon reforming reactions are as follows

1. Dehydrogenation

CH3 CH3

+ 3H2

2. Isomerization
CH3

CH 3 – (CH2 )6 - CH3 CH2 – (CH2)4 - CH

CH3

CH3

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CH3
3. Dehydrocyclization

CH 3 – (CH2 )5 - CH3 + 3 H2

The hydrocracking reactions may also take place. The hydrocracking reactions are
usually undesirable as it result in conversion of useful molecules to low molecular weight
gasses with consumption of significant amount of hydrogen.

CH3 (CH 2 )5 CH3 + H 2 


→ CH3CH 2CH3 + CH3CH 2CH 2CH3

Process

Naphtha reforming involves different types of reactions which are thermodynamically


and kinetically favored at different reaction conditions. For example, dehydrogenations
are favored thermodynamically and kinetically at high temperature and low pressure
while isomerization is kinetically favored at high temperature and pressure. The high
temperature can cause excessive dehydrogenation especially of aromatics in the feed
leading to high rates of formation of coke. To minimize the coke formation, the hydrogen
is added in large excess to feed. The naphtha feed is initially hydrotreated to remove
sulfur and nitrogen compounds as the reforming catalyst are sensitive to these
compounds. The naphtha reforming process is therefore carried out in series of different
reactors to optimize various reactions. Typically the process involves three reactor setups.
The 1st reactor is designed for dehydrogenation of naphthenes to aromatic. The 2nd
reactor is designed for additional dehydrogenation with isomerization and the 3rd reactor
is for dehydrocyclization reactions which are kinetically least favorable and therefore
require large bed volume. The reactors are loaded with increasing amount of catalyst and
the last reactor contains the largest amount of catalyst. Depending on feed the
commercial reformers are operated at 5-35 atm and 450- 500 oC Due to endothermic
reactions, the exit stream from each adiabatic reactor needs to be reheated to 500 0C
before entering the next reactor.

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Fig. 1. Schematic diagram for naphtha reforming process

Catalysts

Reforming catalysts involve dual functions; acidity and dehydrogenation function. The
acidic center of the catalyst promotes the structural changes involved in isomerization
reactions. The dehydrogenation reactions are catalyzed by metal site of the catalyst.
Reforming catalyst usually contains Pt as the metal component and modified γ-Al2O3 as
the source of acidity. The acidity of the Al2O3 is further enhanced by incorporation of
chloride ions into its structure. Addition of small amount of Re along with pretreatment
with H2S improves the life of the catalyst. Re sulfide breaks up the Pt metal surface into
smaller entities and decreases the probability of coke formation. Other promoter such as
Ge, Tr and Sn have also been used in place of Re depending upon feed or process
condition.

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Mechanism and kinetics

Reforming involves simultaneous occurrence of several reactions thereby making


mechanism of reforming very complex. Lumped kinetic models are used in which
naphtha components are lumped into functional groups i.e. alkanes, naphthenes and
aromatics. Some of the reaction scheme used to develop catalytic reforming kinetic
model is shown in Fig.2

(a) (b)

Fig.2. Reaction scheme for catalytic reforming [1]

Deactivation

Major sources of deactivation are:

– Coke formation

– Sintering

– Poisoning by S,N compounds

– Poisoning by Arsenic, Lead, other metals ( Cd, Cr, Co, Fe etc.); As< 1ppb; Pb< 20 ppb
; other metals < 600 ppm

Coke formation is highest in the last reactor. The feed is hydrotreated to remove sulfur
and nitrogen compounds.

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Isomerization

Isomerization involves conversion of less useful hydrocarbons to their corresponding


more desirable isomers. For example, normal butane, pentane or hexane can be isomerizd
to their branched isomers having higher octane number. Similarly, m-xylene can be
isomerized to para-xylene (p-xylene) which is used as feed for production of pure
terephthalic acid. Consequently, out of all the xylenes, p-xylene has the largest
commercial market.

Reactions & Process conditions

The isomerization reactions of butane, pentane and hexane are as follows.

CH3

CH3 (CH2)2 CH3 CH CH3

CH3

CH3

CH CH2 CH3
CH3 (CH2)3 CH3
CH3

CH3

CH3 (CH2)4 CH3 CH3 C CH2 CH3

CH3

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Reaction scheme for xylene isomerization is shown below.

CH3 CH3
CH3

CH3
+

CH3
CH3

m-Xylene
M-Xylene P-Xylene
p-Xylene
O-Xylene
o-Xylene

Isomerization of xylene is carried out at 400-450 0C and 10-20 H2 atm over platinum
based catalysts and equilibrium distribution of different xylene isomers is obtained. The
branched products of the isomerization reactions are thermodynamically more favorable
at lower temperature. The most active catalysts are strong acids such as anhydrous AlCl3
which are also corrosive. Solid catalysts such as Pt/Cl͞ /Al2O3 are also used although have
lower activity at lower temperature.

A typical process flow diagram for isomerization of C5 and C6 alkanes to branched


products is shown in Fig 2. The process conditions of C5/C6 isomerization depend on the
activity of the catalyst as well as on the composition of the feed. For example, feed rich
in hexane requires high hydrogen pressure (~35-100 atm) to maintain low coke formation
where as pentane rich feed can be processed at lower pressure (less than 27 atm) at
temperatures between 120- 175 oC. The feed is mixed with hydrogen to minimize the
coke formation and passes through the reactor followed by separator. The hydrogen from
separator is recycled. The product is further stabilized by removing lighter gases. The
products are separated from the reactants to maintain a favorable equilibrium and the
unreacted normal hydrocarbons are recycled. Any isopentane retained in feed or recycle
is immediately separated at the front end of the process as shown in the figure.

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Fig. 2. Process flow diagram for isomerization of C5 and C6 alkanes to branched products

Catalysts

Initially, Pt supported on Al2O3 – SiO2 was extensively used as the isomerization catalyst.
More recently, Pt- ZSM5 zeolite has proved to be a better catalyst. Pt centers
dehydrogenate the alkanes while acid sites isomerize the resultant alkenes which are then
rehydrogenated by Pt to isomerized alkanes. Pt also serves to moderate the coke
formation by hydrogenation of coke precursors.

Mechanism and kinetics

Isomerization of C4 - C8 hydrocarbons occurs through carbenium ion intermediate. Both,


empirical power rate law and Langmuir–Hinshelwood type of kinetic models have been
used to model the kinetics.

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Catalysts deactivation

Catalysts are mainly deactivated by coke deposition. Coke deposition can be minimized
by increasing H2 pressure. The catalysts can be regenerated by controlled burning of
coke. Other poisons such as sulfur compounds, water and traces of aromatics can also be
removed during coke burn off. The adsorbed sulfur and water on the catalyst can also be
removed by decreasing their partial pressures in the stream, when they are reversibly
adsorbed.

Hydrotreating

Hydrotreating is the process of removal of organic sulfur, nitrogen, oxygen and metals
from petroleum crude at high hydrogen pressure. This process is also used for
hydrogenation of unsaturates. Examples of sulfur, nitrogen and metal containing
compounds as found in pertoleum crude are shown in Fig 10. Importance of
hydrotreating is increasing due to decrease in availability of light and sweet crudes.
Heavier crudes contain more sulfur, nitrogen and metal compounds requiring increasing
treatment for removal of these compounds which act as poison for downstream processes.
More and more stringent emission standard for sulfur and nitrogen content in fuels is
another reason for higher interest in hydrotreating processes.

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Benzonaphthothiophene Benzothiophene Dibenzothiophene

Methyldibenzothiophene Pyridine Acridine

Quinoline Phenanthridine Carbazole

Me= Ni or V

Fig. 10. Examples of sulfur, nitrogen and metal containing compounds in petroleum crude

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Reactions involved

The main reactions that are involved during hydrotreating processes are:

1. Hydrodesulphurization (HDS) : HDS can occur by direct removal of sulfur as H2S


or unsaturated complex molecule may initially undergo partial hydrogenation
followed by sulfur removal.
RSH + H 2  RH + H 2 S

CH 3 − S − C4 H 9 + 2 H 2  CH 4 + C4 H10 + H 2 S

2H2
+ H2S

3H2

S S
CH3 C2H5 CH3 C2H5

H22H2

CH3

+ H2S

C2H5

Among the sulfur compounds the approximate order of activity is RSH > R-S-S-R´> R-S-
R´ > thiophenes. The reactivity of thiophenes decreases in the order thiophene >
benzothiophenoe > dibenzothiophene > alkyl-benzothiophenes. The 4,6
dibenzothiophene is the most refractory of the sulfur compounds hence, most difficult to
be removed.

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2. Hydrodenitrogenation (HDN) : This involves removal of nitrogen compounds


Almost all of the nitrogen in petroleum is present in form of ring compounds. These must
be saturated and opened before the nitrogen can be removed.

+ H2
+ 3H2 + H2 C5H11NH2 C5H12 + NH3
N
N H

CH 3

2H2 H2

N N NH2

H2
3H2

CH 3

+
H
NH3
H2

CH3

NH

H2

CH3

+ NH3

3. Hydrodemetalation (HDM) : Ni, V, Fe removal


NiEP → NiEPH 2 → Ni NiEP : nickel etioporphyrin

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Process conditions

Hydrotreating process condition though depends on feed properties but generally carried
out in temperature range of 300-450 0C at 40-150 atm H2 pressure. The heavier petroleum
feed require more severe conditions and removal is also less efficient compared to light
petroleum feed.

Catalysts

For HDS process, sulfided 2-3 % Co -12-15% Mo supported on Al2O3 catalysts and for
HDN process 2-3 % Ni 12-15% Mo/Al2O3 catalysts are reported to be more active. For
HDM process MoS supported on large pore Al2O3 is suitable. Boron, phosphorus and
potassium are frequently used as promoters. Addition of phosphorous increases the
activity for HDN.

Deactivation

Deactivation occurs through poisoning and plugging of pores by metal. This can be
minimized by stage wise HDM/HDS with moving bed where fresh/regenerated catalyst is
added from top and deactivated catalysts are removed from bottom. Formation of coke
which is another major source of deactivation can be controlled by periodical burning off.

Book reference:

• C. H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic


Processes, Wiley, VCH, 2006
Journal reference

1. M. A. Rodríguez, J. Ancheyta, Fuel 90 (2011) 3492–3508

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Lecture 29

Environmental catalysis

Environmental catalysis involves reduction in emission of SOx, NOx, COx and volatile
organic materials. The sources of these pollutants include mobile sources such as exhaust
gases from automobiles and stationary sources such as exhaust gasses from various
industries. Removal of these gases is done by catalytic treatment of the exhaust gas.
Some of the processes will be discussed here.

Catalytic converter

The pollutants from automobile exhaust gasses are removed by passing the gases through
the catalytic converter. Automobile combustion processes generate large quantities of
CO2 and H2O. However, significant amount of CO and unburned hydrocarbons (HC) are
also produced due to inefficiencies of combustion processes. NOx is produced due to
high temperature reaction between N2 and O2 of air. The quantity of each pollutant varies
with the air to fuel ratio (A/F) used.

CO and HC concentration can be reduced by oxidizing it to CO2 and H2O while NOx is
reduced to N2.

NOx reduction readily occurs at fuel rich conditions, whereas CO and HC oxidations
occur at air rich conditions. However, there exists a narrow window (A/F =14.55 ± 0.1)
in which 90% NOx is reduced to N2 and 90% CO and 85 % HC are oxidized to CO2 and

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H2O. Controlling the A/F ratio within this narrow window is critical for efficient
conversion and done by using O2 sensor placed immediately before the exhaust manifold.

Catalysts

At specific stoichiometric value of air- to- fuel ratio using a selective catalyst all the three
pollutants, CO, NOx and unburned hydrocarbons, can be removed. The catalyst used for
promoting these three reactions simultaneously is known as a three way catalyst. These
catalysts consist of cellular monoliths with parallel open channels. Details about auto
exhaust catalysts are given by Heck and Farrauto [1]. Ceramic monoliths are shown in
Fig 1. These monoliths have large open frontal area (~ 70 %) resulting in low pressure
drops and unrestricted flow. The monoliths are usually made of cordierite having
composition of 2MgO.5SiO2.2Al2O3 . Typically, the monoliths that are used in
automobiles, contains 60-65 cells /cm2. Monolith catalyst is mounted in a stainless steel
container wrapped with matting material. Converters are generally of 10-12 cm diameter
and 7-10 cm long.

Fig. 1. Ceramic monolith

The typical composition of three way catalysts as defined above is shown in Fig. 2.

Three way
catalysts

Active metal Supports Stabilizers


0.1-0.15% CeO2 (10-20%) - 1- 2 % La2O3
precious metals Al2O3 and/or BaO
Fig. 2. Typical composition of three way catalysts

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The alumina-ceria is deposited on monolith honeycomb by dipping the monolith in the


slurry of the components. Alumina washcoat is chemically and physically bonded to the
surface. Washcoat is generally about 15 wt% of the finished honeycomb catalysts.

Pt and Rh are used as active metals. Pt is active for oxidation reactions but converts NOx
to NH3. Rh is highly selective for NOx to N2. A bimetallic catalysts with Pt : Rh ~ 5:1
ratio is generally used. CeO2 act as O2 storage component and liberates or absorbs O2
during air to fuel perturbations according to the following reactions.

rich conditions : CeO2 + CO → Ce2O3 + CO2


lean conditions : Ce2O3 + 0.5O2 → CeO2

CeO2 also act as steam reforming catalysts.

CO or HC + H 2O 
CeO2
→ H 2 + CO2

This H2 reduces a portion of NOx to N2

Kinetics and mechanism

According to Bunluesin et al.[2], mechanism of CO oxidation is significantly affected by


CeO2. In the absence of CeO2, oxidation of CO over Rh/Al2O3 is modeled as

CO + M  CO − M
O2 + M  O2 − M
O2 − M + M  2O − M
CO − M + O − M  CO2 + 2 M

k PO2
Here M is the adsorption site. The rate of CO oxidation is given as r =
PCO
PO2 is partial pressure of oxygen and PCO is partial pressure of CO.
While mechanism pathway in presence of Rh/CeO2 is

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CO + M  CO − M
O2 + 2 M  2O − M
O − M + Ce2O3 → 2CeO2 + M
CO − M + 2CeO2 → CO2 + Ce2O3 + M

Here M is the adsorption site and rate of CO oxidation is given as r = k PO1/2


2

Hence, rate is independent of CO partial pressure in the presence of ceria. At high


conversion, rate becomes limited by external mass transfer. The rate of CO2 formation

over Pt catalyst has been modeled based on Langmuir-Hinshelwood models. According


to Liu et al. [3], CO and O adsorb on adjacent sites on Pt surface. Considering surface
reaction between adsorbed CO and O to be the rate-controlling step, the rate expression is
obtained as :

kPCO PO1/2
r= 2
2
1 + K O1/22 PO1/2
2
+ K CO PCO 

where k is forward rate constant for generation of CO2 . The KO2 and KCO are adsorption
constants for O2 and CO, respectively.

Deactivation

At temperatures above 800 0C in oxidizing atmosphere, Rh can react with Al2O3 forming
a less active aluminate. Poisoning by SO2 may also occur to some extent.

Selective catalytic reduction of NOx

NO and NO2 are undesirable by-products of combustion of fuels in boilers, engines and
turbines as well as in chemical operations such as HNO3 production. In selective
catalytic reduction (SCR) process, ammonia is reacted selectively with NOx to produce
N2 without consumption of excess oxygen.

4 NH 3 + 4 NO + O2 → 4 N 2 + 6 H 2O
4 NH 3 + 2 NO2 + O2 → 3 N 2 + 6 H 2O

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The process is associated with the following side reactions

1. Oxidation of SO2 if any present.


2 SO2 + O2 → 2 SO3

2. Oxidation of ammonia
4 NH 3 + 5O2 → 4 NO + 6 H 2O
4 NH 3 + 3O2 → 2 N 2 + 6 H 2O

Selectivity for these different reactions depends on catalyst and operating conditions.

Catalysts

Different types of SCR catalysts are used such as Pt, V2O5/TiO2 and Zeolites. Each of
these catalysts has different maximum NOx conversion temperature and operating
window. Pt is active in the temperature range of 100-250 0C while zeolite is active at
temperatures greater than 400 0C. Most common catalyst is V2O5 supported on TiO2. Its
operating temperature is in the range of 300 - 400 0C. Here vanadia is the active metal
and titania stabilizes the vanadia. WO3 or MoO3 promoters are added to increase the
activity while significantly decreasing SO2 oxidation activity. SCR of NOx with
ammonia is also carried out with structured monolith based catalysts. For monolith
catalyst based process, the pressure drop is lower, resistance to attrition is higher and
surface area per volume of catalyst is higher compared to fixed bed. The monolith is
usually wash coated with a porous support material such as zeolite or carbon along with
incorporation of the active phase. V, Fe or Mn is used as the active phase.

Kinetics and mechanism

Dumesic et al. 1993 [4] proposed following three step mechanism for SCR of NO with
ammonia on V2O5/TiO2.

NH 3 + M  NH 3 − M
SO + NH 3 − M  NH 2 M + SOH
NO + NH 2 M → N 2 + H 2O + M

M = ammonia adsorption site = acidic site


SO = reactive site on which ammonia is activated = H abstraction
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The third step that is the reaction between NO and NH2M is the rate determining step.
The derived rate expression is

K1 PNH3 / PNO K1 = k2 K NH3 / k3


rNO = k3 PNO
1 + K1 PNH3 / PNO + K 2 PNH3 K 2 = k−2 / k3

Deactivation

Fouling or solid deposition of side products such as fly ash or ammonium bisulfate on the
catalyst surface results in catalyst deactivation. Ammonium bisulphate is formed by the
reaction of SO3 (from SO2 oxidation) with unconverted ammonia. It is a sticky corrosive

compound and causes fouling of heat exchangers and other equipment downstream.
Another cause of deactivation is sintering of titania. Abrasion, fouling and/or poisoning
by fly-ash can be prevented by installation of an electrostatic precipitator. Fouling by SO3
can be minimized by keeping the SO3 concentration low by using lower activity catalyst
or by maintaining the temperature lower than 350 0C or using monolith catalysts which
lower the residence time. Sintering can be minimized by addition of promoter.

Book reference:

• C. H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic


Processes, Wiley, VCH, 2006
Journal reference :

1. R. M. Heck, R. J. Farrauto, Applied Catalysis A: General 221 (2001) 443–457


2. T. Bunluesin E. PutnaR. Gorte, Catal Lett,, 41 (1996) 1-5
3. J.Liu, M.Xu, K.Zaera, Catal Lett,, 37 (1996) 9
4. J.A. Dumesic, N.Y. Topsoe, T. Slabiak, P. Morsing, B.S.Clausen, E.Törnqvist,
H.Topsøe, Proceedings 10th International catalysis Congress ,1993,Elsvier Vol B
1325-1337

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Lecture 30

Hydrogenation and dehydrogenation


Hydrogenation and dehydrogenation are the oldest catalytic processes. Catalytic
hydrogenation reactions are used for production of fine chemicals, in pharmaceutical
industry and polymer industry and for the production of edible and non edible fats and
oils. Dehydrogenation reactions are used for production of light alkenes( C3-C4) for
preparation of acrylonitrile, oxoalcohols or propylene oxides and production of C4 - C8
for detergents. The process is also used for preparation of polypropylene, styrene,
aldehydes, ketones etc.

Hydrogenation

Some of the hydrogenation processes are :

1. Hydrogenation of alkenes and alkadienes

– Catalysts : Raney Ni, Ni/Al2O3, Pt/C, Pt/Al2O3


– Temperature : 50-150 0C
– Pressure : 5-10 atm H2
– Amount of catalysts: 2-5 by wt %
Example

a. hydrogenation of ethene to ethane


C2H4 + H2 = C2H6

b. hydrogenation of cyclohexene to cyclohexane

C6H10 + H2 = C6H12

2. Hydrogenation of aromatics
– Catalyst - Raney nickel
– Temperature – 180-230 0C
– Pressure – 20- 50 atm H2
Example : Benzene to cyclohexane which is the precursor for nylon polymer.

C6H6 + 3 H2 = C6H12

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3. Hydrogenation of nitrobenzene
Hydrogenation of nitrobenezene shows how a wide variety of products can be
obtained by using different catalysts and reaction conditions.

C6 H 5  NO 2 + 3 H 2   Pd/C
50 0C, 75psig
→ C6 H 5  NH 2 + 2H 2O

C6 H 5  NO 2 + 2 H 2    Pt/C


85 0C, 150psig, DMSO solvent
→ C6 H 5  NHOH + H 2O

C6 H 5  NO 2  Pt/C


150 0C, 15-45 psig, H SO
→ C6 H 4  NH 2 OH
2 4

Catalysts

Hydrogenation catalysts can be grouped in two categories as shown in Fig 1. Wide


variation in commercial catalysts is available. Surface area, pore structure and presence
of surface functional groups in supports greatly influence catalyst properties.

Hydrogenation catalysts

Supported transition [Gr VIII]


Supported noble metals
metals

Ni : Most used
METALS : Pd, Pt, Rh, Ru
Cu, Cr, Co: for selected process
Supports :
alumina , activated carbons
Supports : alumina, Silica, MgO,

Carbon supports made from


wood, coals, nuts etc
Surface area : 500- 1500 m2/g

Fig. 1. Catalysts design for hydrogenation catalysts

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Raney Ni

Raney Ni is a very important hydrogenation catalyst. Uniqueness of this catalyst is that it


is a bulk unsupported catalyst with high surface area. The advantages include absence of
support, minimum side reactions and more easy reduction of Ni in absence of interaction
with supports. Raney Ni is typically prepared by the following steps:

1. Bulk Ni and Al metals in a 50-50 mixture are melted together.


2. Molten metals are poured into water producing fine grains
3. 20 % NaOH is added to leach Al from alloy leaving a porous matrix rich in Ni
90-95 % with a high surface area ~ 100 m2/g
4. Raney nickel is stored in an inert atmosphere such as water or fat oil to prevent
reoxidation

H--H H--H
H H

Pt Pt Pt Pt Pt Pt

Support Support Support


Fig. 2. Dissociative adsorption of hydrogen over Pt active site

Kinetics and mechanism

During hydrogenation of alkene over noble metal based catalysts, at first hydrogen get
adsorbed dissociatively on the metal sites (Fig. 2). Dumesic et al. [1] reported that
adsorption of hydrogen follows different kinetics at low alkene coverage and at high
coverage. For hydrogenation of ethylene two types of site for hydrogen adsorption was
proposed. The proposed mechanism is shown below. The two types of site for hydrogen
adsorption are represented by ‘S’ and ‘*’.The site for adsorption of hydrogen on a
surface partially covered with ethene was represented as ‘S’, whereas hydrogen
adsorption site on a clean surface was designated as ‘*’. At adsorption sites, ‘*’ , both the
hydrogen and ethene can get adsorbed but at ‘S’ site only hydrogen can adsorb.

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(1) H 2 + 2S  2H − S occurs on surface covered with ethene


(2) H − S + S'  H − S'+ S
(3) C2 H 4 + 2*  C2 H 4 **
(4) C2 H 4 ** + H − S'  C2 H 5 ** + S'
(5) C2 H 5 ** + H − S'  C2 H 6 + 2 * +S'
(6) H 2 + 2*  2H * occurs on clean surface
(7) H * +S'  H − S'+ *

Hydrogen adsorbed dissociatively on the Pt surface at ‘S’ or ‘*’ adsorption sites forming
H-S’ or ‘H*’. The adsorbed hydrogen atom ‘H-S’ or ‘H*’ were further assumed to be
activated on another site Sˈas shown by step 2 or 7. The activated hydrogen H-Sˈ then
can react with C2H4** to give C2H5** (step 4) and then with C2H5** to give C2H6 (step
5). The Step 5 was considered as slowest and rate determining step.

Hydrogenation of organic compounds is usually conducted in liquid phase in a slurry


reactor. Most hydrogenation reactions are highly exothermic and hence careful
temperature control is required. Solvent is used to affect the product selectivity and to
absorb the liberated reaction heat. Hydrogenation reactions in the slurry reactor are
typically limited by mass transfer of H2 from gas bubbles through liquid to each
suspended catalyst particle. For hydrogenation reaction to occur, the hydrogen has to be
transported from bulk phase to liquid phase through gas – liquid interface and then from
bulk liquid to surface of solid catalyst for final reaction. The Fig. 3 schematically shows
the various concentrations of hydrogen at different positions for a single bubble and
particle combination. The Cg, CL and Cs shown in the figure represent concentration of
hydrogen in gas bubble, liquid and catalyst surface respectively.

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Fig. 3. Concentration profile of gaseous reactant in slurry reactor

For first order irreversible catalytic reaction, the surface reaction rate per unit volume of
bubble free slurry may be written as

rv = k a cCs (1)

Where,

a c = external area of catalyst particles per unit volume of liquid (bubble free)
k = first order rate constant
Cs = concentration of reactant (hydrogen) at the outer surface of catalyst particle

The rates of three mass transfer processes for hydrogen may be expressed as

=rv k g a g Cg − Cig  for transport from bulk gas to gas – liquid interface (2)

=rv k La g [ CiL − CL ] for transport from gas – liquid interface to bulk liquid (3)

=rv k ca c [ CL − CS ] for transport from bulk liquid to catalyst surface (4)

where, ag is the gas bubble – liquid interface area per unit volume of bubble free liquid
and kg, kL and kc are the appropriate mass transfer coefficient.

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H2 pressure decreases across the gas film due to film diffusional resistance. At the gas
liquid interface, a concentration of hydrogen in the liquid is determined in accordance
with Henrys law. If equilibrium exists at the bubble-liquid interface Cig and CiL are
related as Cig = H CiL (5)

Where, H is known as Henry´s constant. From equations 1,2,3,4 and 5 the Cig, CiL, CL
and Cs can be eliminated and the rate can be expressed in terms of reactant in gas as

rv = k o a c Cg

Where ko is given as

1 a 1 ac H  1 1
= c + + H + 
ko ag kg ag kL  kc k 

The ko is the function of three mass transfer coefficients, the reaction rate constant and
area ratio of catalyst and gas bubble in contact with liquid. The values of mass transfer
coefficients can be obtained from several correlations available in literature.

Deactivation

Deactivation of catalysts mainly occurs by poisoning of metal surface with sulfur,


halogens, phosphorus and nitrogen compounds. As the hydrogenation reactions occur in
slurry condition, mechanical attrition is another major source of loss of catalysts. In
addition, pore blockage may occur due to coke deposition.

Dehydrogenation

Catalysts

Important catalysts include chromic oxide/alumina and zirconia, Mo/alumina, Pt-


Sn/alumina depending on the type of dehydrogenation reaction. Examples of important
dehydrogenation reactions & catalysts are given below :

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1. alkanes 
Cr/Al2O3
400−600 0 C,1−3atm
→ alkenes

Pt −Sn/Al2O3
2. n-Butane 
500−600 0 C,1−3atm
→ isobutene

Fe 2O3 − K 2O/Cr2O3
3. ethylbenzene 
600−650 0 C, steam
→ styrene

Cu − K/SiO 2
4. alcohols →
250− 400 0 C
aldehyde,ketones

Kinetics and Mechanism

Dehydrogenation reaction can be modeled based on Langmuir-Hinshelwood kinetics. The


Langmuir-Hinshelwood model of isobutane dehydrogenation proposed by Cortright et al.
[2] for Pt-SnO2 based catalysts is given as

(1) C4 H10 + 2*  C4 H 9 * + H *
(2) C4 H 9 * +2*  C4 H8 ** + H *
(3) C4 H8 **  C4 H8 + 2 *
(4) H 2 + 2*  2H *

Where ‘*’ is the active site. The second step of dissociative adsorption of isobutane is
the slow and rate determining step. The corresponding rate expression is given as

 PiC4H8 PH2 
rDH =
kθ*2  PiC4H10 − 
 K eq 

where rDH is the net dehydrogenation rate, k is the rate constant for the dissociative
adsorption of isobutane, Keq is the overall equilibrium constant for isobutene

dehydrogenation, and θ* is the fraction of sites that is free of adsorbed species.

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Deactivation

Main problem for dehydrogenation reaction is rapid deactivation by coke deposition


requiring very frequent regeneration.

Oxidation reaction

Oxidation processes consist of oxidation of inorganic compounds and partial oxidation of


organic compounds. Oxidation of inorganic compounds is used to produce chemical feed
stocks and is among the oldest and largest processes. Production of sulphuric acid by SO2
oxidation and nitric acid by ammonia oxidation are amongst the major basic chemical
industry. Oxidation processes will be illustrated by few examples.

Oxidation of inorganics

SO3 production

SO2 is oxidized to SO3 which is further converted to sulphuric acid. This process is one
of the highest tonnage processes in the world.

SO2 + ½ O2 = SO3

Catalyst for this process is vanadium potassium sulfate supported on silica rich carrier
such as natural clay. Minimum inlet temperature required for vanadium based catalysts is
400 0C. For single pass operation at 400 0C, the temperature rises to 600 0C and the
conversion is limited to 60% by equilibrium. Therefore, multiple pass reactors, with
intermittent heat exchange, is used to achieve near 100 % conversion.

Mars and Maessen [3] proposed a two step redox mechanism as shown below. Second
step is the rate determining.

SO 2 + 2V 5+ + O 2−  SO3 + 2V 4+
2V 4+ + 0.5O 2 → 2V 5+ + O 2−

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Using Langmuir-Hinshelwood model, rate is given as


l
k PSO Pm Pn
r= 2 O 2 SO3

(1 + AP SO 2 + BPO2 + CPSO3 )
Where l and m lie between 0.5 to 1 and n lies between -1 to 0.

Partial oxidation of organics

Methanol to formaldehyde

Methanol is partially oxidized to produce formaldehyde. Formaldehyde is used for


production of urea, disinfectant, preservative etc.

CH3OH + 0.5 O2 = HCHO + H2O

The process is carried out at 600-700 0C temperature at near atmospheric pressure using
silver needles or gauges catalysts. As a result of high process temperature, the
unsupported silver catalyst tends to sinter resulting in increased pressure drop and
reduced activity. To minimize these adverse effects without compromising adequate
contact of reactants with the catalyst, a shallow (4 to 5 cm thickness) but wide bed (~ 3m)
of Ag needles or gauge is used. The unsupported silver catalyst is sensitive to S, N, halide
compounds. Methanol oxidation process at dilute condition is carried out over Fe2O3-
Co2O3-MoO3 catalyst at lower temperature of 300 – 400 0C at atm pressure.

Ethylene to ethylene oxide

Ethylene oxide is used to produce ethylene glycol. Polyethylene glycols are important
monomers for liquid plasticizers, lubricants. Ethylene oxide is produced by partial
oxidation of ethylene and is a highly exothermic process. Process is carried out at 200 –
250 0C temperature over silver supported on alumina catalysts. The process is always
associated with secondary oxidations of ethylene oxide (equation 6) or total oxidation of
feed to carbon oxides and water (equation 7) as shown below. This can be minimized by
controlling process conditions and proper catalyst selection.

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=
CH 2 CH 2 + 0.5 O 2 →
Ag
CH 2OCH 2 
→ CO 2 + H 2O
(6)
undesired secondary oxidation

=
CH 2 CH 2 + 3O 2 →
Ag
2 CO 2 + 2H 2O undesired total oxidation (7)

Kinetics and mechanism

Ethylene oxide formation over silver catalysts is proposed to occur through dissociative
chemisorption of oxygen. The proposed mechanism by Haul and Neubauer [4] is as
follows :

Ethylene oxide formation pathway :

O2 + S  S − O2
S − O 2 + S  2S − O
C2 H 4 + S − O → S − O − C2H 4
S − O − C 2 H 4 → S + C 2 H 4O

Total oxidation pathway :

S − O − C2 H 4 → S − O − CHCH 3
S − O − CHCH 3 + 5O − S → 6S + 2CO 2 + 2H 2O

Park and Gau [5] proposed a Langmuir –Hinshelwood rate expression for supported
silver over barium doped silica as r =
k1K E K O PE PO
(1 + K E PE + K O PO )
2

Here E = ethylene and O = oxygen

Deactivation

Unsupported silver catalysts are very sensitive to poisoning by S, N and halide


compounds. Very high temperature also results in fusion of silver catalysts. Catalysts life
for of silver catalysts is only 6 months. Fe2O3-Co2O3-MoO3 is more rugged and lasts for
about 1-2 years.

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Book reference:

• C. H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial catalytic


Processes, Wiley, VCH, 2006

Journal reference :

1. J.A . Dumesic, D.F Rudd, L.M Aparicio , J.E. Rekoski and A.A. Trevino , The
microkinetics of heterogeneous catalysis, ACS ,1993
2. R.D. Cortright, Per E. Levin, J. A. Dumesic, Ind. Eng. Chem. Res. 1998, 37, 1717-
1723
3. P. Mars and J.G. Maessen , J. Catal. 10 (1968) 1257
4. R. Haul and G. Neubauer J. Catal. 105 (1987) 39
5. D.W. Park and G. Gau, J. Catal. 105(1987) 81

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